Gel type polymer electrolytes with PVDF-HFP as polymer host, NaI salt and EC/PC as plasticzers have been prepared and optimized for use in a dye sensitized solar cell. The polymer electrolyte containing 48 wt. % (PVDF-HFP)–32 wt. % NaI–20 wt. % (EC/PC) exhibits a room temperature conductivity of 1.53 × 10−4 S cm−1. The maximum conductivity is associated with maximum amorphousnous (confirmed by X-ray and FTIR) of the electrolyte and increase in carrier density. DSSCs have been fabricated with the highest conducting (PVDF-HFP)-NaI-(EC/PC) gel type polymer electrolyte containing iodine/triiodide redox couple using natural dye sensitizers, anthocyanin from black rice extract, chlorophyll from pandanus amaryllifolius extract and the mixture of the two dyes and their performances were compared. For individual dyes, DSSC with anthocyanin has shown better performance than the DSSC using chlorophyll dye. The DSSC with the dye mixture exhibits better performance than both individual dyes with a short-circuit current density of 2.63 mA cm−2, open-circuit voltage of 0.47 V, fill factor of 0.58 and the highest photo-conversion efficiency of 0.72% under the illumination of 100 mW cm−2 white light. Under illumination of lower light intensity of 60 mW cm−2 and 30 mW cm−2, the fill factor enhanced from 0.58 to 0.59 and 0.6 and the photoconversion efficiency increased from 0.72% to 1.11% and 1.85% respectively.