Two dimensional rGO was decorated over circular-bipyramidal structure of PPY-TiO2 by chemical oxidative polymerization of pyrrole monomer. The structural analysis of PPY, GO, TiO2, PPY-TiO2 and PPY-TiO2-rGO nanocomposite was observed by XRD, FESEM and TEM analysis. Inflated non-radiative electron-hole recombination rate and lower value of decay time with better thermal stability were observed for PPY-TiO2-rGO nanocomposite. Enhanced current density (~ 300%), optimized low band gap (~ 1.32 eV), high dielectric constant and high specific surface area were also observed for ternary nanocomposite. The PPY-TiO2-rGO electrode also manifested the high specific capacitance value (~ 1171 F/g) and high discharge time (~ 3450 s) with high electrochemical reduction potential (~ +0.610 V). These increased rates of non-radiative recombination, reduced band gap, enhanced conductivity and thermal stability, high values of dielectric constant, improved electrochemical reduction potential, augmented specific capacitance, high discharge time and power density (~ 799.74 W/kg) with scant loss in energy density at high current density proposed that, PPY-TiO2-rGO nanocomposite can be employed as electron transport layer (ETL) material in OLED devices and supercapacitor electrode material.