Poly(methyl acrylate) (PMA)-tetrapropylammonium iodide (TPAI) and poly(vinyl acetate) (PVAc)-TPAI solid polymer electrolytes were prepared by solution casting method. DSC, FTIR, and conductivity results are reported. TPAI interacts with PMA and PVAc to form PMA-TPAI and PVAc-TPAI complexes. Formation of PMA-TPAI and PVAc-TPAI complexes are supported by the DSC and FTIR studies. Linear relationship for the dependence of glass-transition temperature, T g , on salt concentration allows the estimation of the complexation extent between polymer and salt. A greater extent of complexation for PMA with TPAI is observed and correlated with the FTIR results. The conductivities achieved at 15 wt % of TPAI for PMA and PVAc are 2.6 × 10 −11 and 1.3 × 10 −11 S cm −1 , respectively. Higher dielectric constant and lower T g of PMA result in higher number and mobility of ions, which lead to higher conductivity in accordance with σ = enμ. All-solid-state dye-sensitized solar cells (DSSCs) were assembled with PMA-TPAI and PVAc-TPAI electrolytes. DSSC efficiencies achieved for PMA and PVAc are 2.41% and 2.05%, respectively. Better performance of DSSC with PMA electrolyte is attributed to higher short-circuit current density, J sc , and lower recombination loss. Lower J sc , higher recombination loss, and degradation of counter electrode are the reasons for DSSC degradation.