Abstract High performance polymer electrolyte for dye sensitized solar cell application has been prepared using suitable polymer matrix reinforced by reduced graphene oxide (RGO) nanosheets. RGO nanosheet has been synthesized using appropriately modified Hummer’s method. The matrix has been formulized as an optimized blend of polyethylene oxide and polyvinylidene fluoride – hexafluoro propylene (PEO/PVDF-HFP) to get expected high performance characteristics in terms of ionic conductivity, charge carrier concentration and diffusion coefficient. The same has been confirmed using electrochemical impedance spectroscopy and linear steady state voltammetry. Excellent stability of the electrolyte also has been recorded through efficiency retention study. Further, solar cell has been fabricated using the optimized formulation of PEO/PVDF-HFP/RGO nanosheet polymer electrolyte. The optimum performance in comparison with liquid electrolyte based solar cell has been authorized through photo voltaic performance study in terms of open circuit voltage (Voc), short circuit current (Jsc) and solar conversion efficiency.