This study investigates the impact of small cations on improving conductivity and efficiency of dye-sensitized solar cells (DSSCs). The work includes preparation and characterization of polyvinyl alcohol-based gel polymer electrolytes (GPEs) containing tetramethyl ammonium iodide (TMAI) and potassium iodide (KI) salts. The degree of crystallinity of the GPEs has been determined from x-ray diffraction (XRD). From electrical impedance spectroscopy (EIS), the gel polymer electrolyte with only TMAI salt exhibits a conductivity of 1.72 mS cm⁻¹. On addition of KI salt, conductivity increased up to a maximum of 7.87 mS cm⁻¹ for the GPE comprising 70 wt. % KI. The dye-sensitized solar cells (DSSCs) with GPE comprising 100 wt. % TMAI – 0 wt. % KI exhibits a short-current density, J_sc of 6.60 mA cm⁻² and open-circuit voltage, V_oc of 0.56 V. The fill factor, ff, and efficiency, η, obtained are 79% and 2.92%, respectively. The existence of a small cation K⁺ in the GPE enhances DSSCs performance with GPE consisting of a 3:7 weight ratio between TMAI and KI exhibits J_sc of 11.30 mA cm⁻² and V_oc of 0.60 V. The acquired fill factor, ff, and efficiency, η, are 74% and 5.02%, respectively.