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. © 2020 by the authors.