AbstractDeveloped specifically to address leakage and stability concerns inherent in liquid electrolytes, this study presents a significant advancement in polymer gel electrolyte (PGE) formulation by combining potassium iodide (KI), ammonium iodide (AI) salts, and polyvinylidene fluoride‐co‐hexafluoropropylene (PVDF‐co‐HFP) as a host polymer. The tape casting method was employed to deposit the standard TiO2 paste as the photoanode and platinum paste as the counter electrode. N3 dye was incorporated, and PVDF‐co‐HFP was used as the PGE between the electrodes. The conductivity of PGE was measured by using a digitized conductivity meter. The quasi solid‐state solar cell (QS‐DSSC) assembled using single salts (KI, and AI), and mixed cations PGE was examined via photocurrent–voltage characteristics, and electrochemical impedance spectroscopy. The augmented ionic conductivity directly influences the efficiency of DSSCs. Notably, incorporating a mixed salt (KI + AI) within the PGE enhances ionic conductivity compared to single‐salt‐based counterparts. The resultant DSSCs using mixed salt PGE exhibit a Voc of 600 mV, Jsc of 1.01 mA/cm2, FF of 0.6089, and an efficiency of 0.369%, outperforming those using KI or AI. This highlights the perceptible advantages of employing this innovative electrolyte composition to enhance solar cell performance.