Although the use of quasi-solid electrolytes in dye-sensitized solar cells (DSSCs) is viewed as a solution to the stability problem of DSSCs, the network structure effect on the DSSCs’ performance has not been studied in detail. Structurally different hydrogels poly (2-methacryloyloxyethyl trimethylammonium chloride-co-acrylic acid) were prepared and used as quasi-solid gel electrolytes in DSSCs to investigate the network structure effect of hydrogels on DSSC performance. The hydrogel’s network structure was changed using different amounts of cross-linkers during synthesis. Five quasi-solid electrolytes were prepared from the hydrogels. The increased cross-linking of quasi-solid electrolytes during synthesis raised conductivity from 0.102 to 0.144 S m 1. Despite expectations, it was observed that the energy conversion efficiency of DSSCs does not follow the rising trend in conductivity, as it rises from 6.57% to 6.62% and then decreases to 5.17%, with increased cross-linking. Moreover, cross-linking during hydrogel synthesis defines not only the electrical properties of quasi-solid electrolytes but also the swelling, wetting, and morphological properties of the structure. Therefore, this study aimed to investigate how and which parameters affect the energy conversion efficiency of DSSCs that are prepared with quasi-solid electrolytes.