Prior to the creation of conducting polymers (conjugate polymers), polymers were thought to be electrical insulators, however, these organic polymers exhibit unique electrical and optical properties that are similar to those of inorganic semiconductors [1]. The highly delocalized, polarized, and electron-dense bonds are responsible for the electrical and optical properties of a conjugated carbon chain, which is made up of alternate single and double bonds. Polyacetylene (PA), polyaniline (PANI), polypyrrole (PPy), polythiophene (PTH), poly(para-phenylene) (PPP), poly(phenylenevinylene) (PPV), and polyfuran are examples of conducting polymers (PF) [2]. Owing to the exclusive properties of copolymers, a sequence of copolymers was made by chemically oxidative polymerization of p-phenylenediamine (pPDA) to advance their properties. The most illustrious of these copolymers with aniline poly(aniline-co-1,4-phenylenediamine). It is motivating to bargain that the electrical conductivity, precise capacitance, and cycling stability of the P (ANI-co-pPDA) copolymer electrode materials were clearly developed with a certain suckling ratio of pPDA, related to those two homopolymers [3]. Using sodium dodecyl sulphate (SDS) as an emulsifier and potassium persulphate as an oxidant, electrically conducting copolymer p-phenylenediamine-co-o-aminophenol and carboxylic acid functionalized MWCNTs [poly(pPD-co-oAP)/c-MWNTs] were synthesized via in situ emulsion route. The tubular shells of the composites were formed using acid-functionalized MWNTs as cores [4]. The poly (p-phenylenediamine-co-o-amino phenols prepared by chemical and electrochemical polymerization technic for corrosion protection of mild steel (MS) in acidic medium.[5]. Owed to the exclusive properties of glycerol (1,2,3-propanetriol), it was added in many uses as fabrication of chemicals and polymers [6, 8]. In the playing field of polymers, glycerol can be useful as a monomer, both in the pure form and as glycerol carbonate and methacrylate, or as an initiator [8, 10].. Due to its high plasticization performance, wide availability, and low exudation, glycerol has been the most commonly utilized plasticizer in polymers[11, 12]. It is also commonly using it as a plasticizer because of its low molecular weight, that when combined with polymers increases the free volume of the material or the macromolecular mobility of the polymer, causing the polymeric network to be less dense resulting in a decrease in intermolecular forces, enhancing the films' stretchability and flexibility [13]. Glycerol have been commonly used as organic solvents and auxiliary electrolytes in many scientific fields due to their admirable properties such as extraordinary conductivity, non-volatility, and non-flammability [14, 15]. The wide range in the use of glycerol is owed to glycerol properties which lessen intermolecular forces and increases the flexibility of the biopolymer chains. It can also modify the mobility of water due to its ability to reduce the surface energy of an aqueous solution [9]. In this paper, we, study the outcome of glycerol in the polymerization of p phenylenediamine with altered ratio (1:1, 1:2, 2:1) and study its influence on thermal behavior and electrical conductivity. Moreover, studying the influence of adding eggshell nano as an eco-friendly material and muli-walled carbon nanotube with different weight % on the behavior of the prepared copolymers nanocomposite.