Benzoguanamine doped 0%, 10%, 20%, 30%, 40% and 50% PVDF/KI/I2 polymer electrolytes were prepared by solution casting technique. The crystallinity, surface morphology, ionic conductivity and photovoltaic performance of polymer electrolytes were analyzed. The PXRD studies have confirmed the decreased and increased crystallinity of benzoguanamine doped polymer electrolytes. The surface morphology of polymer electrolytes is discussed using SEM analysis. From the AC-impedance analysis, ionic conductivity of benzoguanamine doped 0%, 10%, 20%, 30%, 40% and 50% PVDF/KI/I2 polymer electrolytes were calculated as 5.57 × 10− 6 Scm− 1, 1.05 × 10− 5 Scm− 1, 5.95 × 10− 5 Scm− 1, 3.09 × 10− 5 Scm− 1, 1.56 × 10− 5 Scm− 1 and 1.48 × 10− 5 Scm− 1, respectively. The photovoltaic performance of benzoguanamine doped 0%, 10%, 20%, 30%, 40% and 50% PVDF/KI/I2 polymer electrolytes based DSSCs have achieved 1.5%, 1.9%, 2.8%, 2.5%, 2.3% and 2.1% power conversion efficiency, respectively.