A hybrid polymer gel electrolyte (PGE) comprising of polyacrylonitrile (PAN) with graphene incorporated in a mixture of iodide redox electrolyte was prepared for the first time for use in quasi-solid dye-sensitized solar cells (DSSC). The exfoliated 2-D graphenes were dispersed homogenously within the PGE and facilitate the diffusion of I⁻/I₃ ⁻ ion pairs in the electrolyte system. The ratio of graphene in the PAN PGE was optimized to maximize the ionic conductivity and photoelectronic properties of the DSSC. The energy conversion efficiency of the DSSC achieved by using this hybrid PGE with 0.2 wt% Gr is 5.41%, which is 1.5 times the value of the liquid-state cell (3.72%).