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Polymer gel electrolytes based on poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) and poly(acrylonitrile-co-butadiene) (PAB) or poly(dimethylsiloxane) bis(3-aminopropyl)-terminated (PDES-bAP) copolymers were prepared and investigated in dye-sensitized solar cells (DSSCs). Selected optical and electrochemical properties of all compositions with various ratio from 9:1 to 6:4 were investigated towards DSSC applications. The highest value of power conversion efficiency equal to 5.07% was found for DSSCs containing a PVDF-HPF:PAB (9:1) gel electrolyte. Compositions of electrolytes were additionally tested by electrochemical impedance spectroscopy. The influence of the ratio and type of polymers used as an additive to PVDF-HPF on absorption wavelengths, energy gap, and Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) levels were investigated. Individual components of DSSCs, such as the TiO₂ layer and platinum nanoparticles, were imaged by scanning electron microscope. Finally, a DSSC module with six electrically separated solar cells with a 7 × 80 mm² active area was constructed based on gel electrolytes and tested.