Polymer electrolyte films with different weight ratios (10, 20, 30, 40 and 50%) of a manganese-benzene tricarboxylic acid metal-organic framework (Mn-BTC MOF) over a polymer gel electrolyte (CLP+PEO+I₂+TBP+DMII+LI) were prepared using solution casting. A Mn-BTC MOF/CLP–PEO polymer electrolyte film was evaluated for its structural, morphological and thermal properties using Fourier transform infrared spectroscopy, scanning electron microscopy and thermogravimetric techniques. At room temperature, a maximum ionic conductivity of 2.6 × 10⁻³ S cm⁻¹ was observed for polymer electrolyte containing 30% of Mn-BTC MOF with CLP–PEO. The photovoltaic characterization studies of the prepared polymer electrolytes indicate that a higher power conversion efficiency of 5.45% was obtained for 30% of Mn-BTC MOF with CLP–PEO. Hence, these studies conclude that incorporating Mn-BTC MOF into a polymer electrolyte can improve the power conversion efficiency and can be used as a suitable material for dye-sensitized solar cell applications.