The present research, reports the hygrothermal behaviour of poly[ethylene oxide] (PEO) based composite film (500 and1000 µm) containing NH4I and KBr (5–20%) as the mobile phase and non-reactive silica (15wt %) as the filler. These are termed as PK/NSiO2-series for solvent sorbed and (PK/NSiO2)NS for non-swelled film. The novelty of the research lies in the analyses of non-Fickian solvent diffusion trait of films using python programming. The presence of ions and its variable polarizable nature is found to influence the number density of bonded and free solvent content along with the extend of cross linkage. Introduction of silica is found to enhance the ionic conductivity (about one order higher) of the film irrespective of the type of charge carrier owing to the improved dispersion within the matrix. Non-Fickian diffusion is found to influence the ionic conductivity of P2K20SiO2 (10− 5Scm− 1 to 10− 2 Scm− 1) minimizing the endurance to 0.2%ΔC/1000h (> 1%ΔC/1000h, tested for 2000 h) compared to P2N20NSiO2. In contrast, ion migration in P2NSiO2 is guided by Rice and Roth model and being more polarizable ions, the mobility is significant which maximizes the conductivity to ~ 101 Scm− 1. Microstructural study shows heterogenous nucleation to be more pronounced upon addition of silica filler wherein the homogeneity, inter fibrillar interaction and grain growth of spherulites is higher. This tends to extend amorphous regions thereby propagating the ion migration path. The influence of sorption process is studied in terms of electrochemical impedance, dielectric analyses and long term cyclability (20000 h) in terms of loss tangent.