Recently, polyindole (PIN) has been one of the most preferred conducting polymers by researchers worldwide. 1,2 This can be attributed to its intriguing physicochemical, remarkable redox activity and environmental stability. 3,4 As a result, they have been synthesised using several polymerisation techniques including, electrochemical oxidation, 1 chemical oxidative, 5 interfacial, 6 DNA template, 7 and emulsion. 8 Polymerisation of indole (PIN) has also presented several advantages including ease of synthesis, and lower processing costs. Despite this, majority of researchers have termed the synthesis of PIN as difficult. These difficulties include pre and post polymerisation challenges including low yield, 1 inseparable impurities, and irregular morphology. 9 For example, while crystallinity of indole is reduced during polymerisation using established techniques in the presence of organic solvents, the porosity along with dimensional irregularity is also hugely affected and can be evident through multiple reports by researchers 9,10. For instance, Erdonmez et al. (2020), synthesised PIN using chemical oxidative polymerisation using chloroform as solvent, resulted granular structure and irregular morphology. 4 Apart from this, irregular size PIN particles increase internal resistance thereby affecting overall electrical conductivity. This can be attributed to inability of electrolytic ions to efficiently transport through the irregular PIN particles. The ion transport can be affected by multiple factors such as crystal structure and porosity. 11,12 Apart from organic solvents, which are costly and environmentally unfriendly, PIN is also reported to be synthesised in aqueous medium in the presence of surfactant, 13,14 however they also suffered from mixed morphologies which resulted in limited electrochemical performance. 15 Surfactants, are chemical compounds and have been explored for controlling morphological features (tubular, and spherical) through micelle stabilisation. For instance, Unal et al. (2013) reported effect of anionic surfactant SDS in obtaining homogenous sponge-like morphology of PIN/ TiO2 nanocomposite. However, the particulate geometry of the synthesised nanocomposite featured an average particle size of 0.6 microns. 13 In addition to this, thermal stabilities were found to be reduced, and were attributed to decomposed PIN chains owing to the removal of SDS molecules. In another instance, Phasuksom et al. (2016) were able to obtain smaller PIN particles with the help of SDS, however, the SDS remained in the final product, as confirmed by FTIR analysis, suggesting the inseparability of surfactant during post polymerisation processing. 16 Post polymerisation remnants increase post polymerisation processing, which in turn negatively affect the electrochemical performance. All these reports raise a need to find an alternate technique which could remediate above issues thereby enhancing overall electrochemical performance. Our previous work, 17 for the first time introduced the use of hydrotrope – tetra n-octyl ammonium bromide (TOAB), a class of TBAB in terms of structural integrity for synthesis of polyindole in aqueous media. A Hydrotrope is a chemical compound that enhances aqueous solubility of an organic compound. 18 The enhanced aqueous solubility had been attributed to the co-operative solubilisation, which improves the interfacial interaction between inorganic-organic with aqueous medium. 19 Furthermore, its role as phase transfer catalyst and encapsulating agent was also established, owing to which, nano-dimensioned PIN was obtained without any traces of hydrotrope. The hydration effect reduced overall reaction kinetics thereby bringing uniform morphology throughout the material. This was attributed to the regioselective complexes between the TOA– - Indole, TOA – -APS, and TOA – - Br. Although, pristine PIN has been reported to exhibit better electrochemical properties, they have been incorporated with other inorganic metal for enhanced performance. Consequently, several PIN based nanocomposites, owing to their synergistic gains have been explored with several inorganic metal-oxides, hydroxides, metal sulphides and selenides. For instance, Raj et al. (2015) reported PIN-Co3O4 nanocomposite to have enhanced electrochemical properties (such as specific capacitance, rate capability and cycling stability) and attributed to the synergistic effect between Co3O4 and PIN. Similarly, the charge storage performance parameter, defined by the real component (behaviour of the dielectric function in lower frequency region) was found to decrease (lower, the better) with increasing concentration of WO3 in PIN/WO3 nanocomposite, which was attributed to hierarchical interconnectivity network offered by PIN. 4 In another instance, 20 the stability of RuO2 in the ternary composite SWCNT/RuO2/PIN was found to increase owing to the protective nature of PIN in terms of electrochemical stability. Similarly, owing to the physicochemical interactions (such as electrostatic) in nanocomposites (involving hydroxides and sulphides with conducting polymers such as polyaniline, polythiophene etc) resulted in minimal metallic particle agglomeration along with improved electrochemical activity. However, unlike metal oxides and sulphides, transition metal selenides (TMS) offer lower bandgap and weak metal selenium linkage, which can be effectively utilised to enhance redox performance even more. Further, with respect to EDLC, the increased layer spacing also facilitates rapid ion diffusion. These benefits along with its low cost, abundancy, and rich electrochemical activity has been led TMS to be deployed in majority of applications including catalysts, 21,22 water splitting, 23,24 oxygen/hydrogen evolution reactions (OER/HER) 25,26. Among several applications, TMS for energy storage applications (for e.g., supercapacitors) has been seen as promising high performance electrode material recently. 27–29 However their stability has severely limited their electrochemical applications. 27 For instance, TMS suffer sever volume expansion on extended cycles and exhibit poor conductivity in energy storage devices. Hence, to remediate this issue, they have been preferred with reinforcing polymer materials such as conducting polymers (CPs). For e.g., polypyrrole (PPy) coating over CoSe2 has been reported to enhance electrochemical performance of the nanocomposite through high temperature selenization. 30 Other conducting polymers such as with TMS comprised of Co, Ni, Mn has also been explored however to our knowledge, we could not find polyindole based TMS nanocomposites, especially Vanadium selenide (VS). VS has been focussed a lot recently owing to its layered structure and its wide array of applications including energy storage. Apart from this, vanadium also features a low ionisation energy, facilitating easy volunteering in a chemical reaction. Very few studies have featured VS in regard to electrochemical performance, 31 however electrochemical properties of conducting polymer based VS have seldomly explored. As a result, herein we report for the first time, in-situ hydrotopically engineered one pot synthesis of polyindole decorated vanadium selenide (PV) in aqueous medium. VS was synthesised using facile one step hydrothermal technique, and its monoclinic phase was confirmed using XRD technique. PV nanocomposite was then subjected to physicochemical characterisation such as FTIR, FESEM, which validated the decoration of PIN over VS. In addition to this, electrochemical analysis of the nanocomposite over VS through galvanic charging discharging studies revealed enhanced specific capacitance, energy and power density of 318.75 F/g, 102 Wh/kg and 0.8 W/kg, respectively. Furthermore, to complement real time charge storage ability, the as synthesised nanocomposite along with activated carbon was used in fabrication of asymmetric supercapacitor device. The device was connected in series with DC source and was able to illuminate LED, suggesting the conductive nature. Additionally, the device was also connected in series with digital stopwatch which successfully powered for at least 15 minutes.