In this research, gel-state and quasi-solid state dye-sensitized solar cells (DSSCs) were fabricated with polydimethylbenzimidazole(PDMBI) as the polymer electrolyte. These devices are stable under room light in air, even without encapsulation. The energy conversion efficiency of gel-state cells was drastically increased around 200% after the device worked. We propose that appropriately aggregated PDMBI in electrolyte layer could provide pathways which would facilitate the diffusion of ion through the electrolyte. Moreover, this arrangement induces it an ion exchange reaction which could lead to the promotion of the diffusion rate between iodide species. An optimized device performs well with a power conversion efficiency of 4.98% under air-mass 1.5 global (AM 1.5G) illumination. For the fabrication of quasi-solid state dye-sensitized solar cells, we immersed a few liquid electrolyte to improve electrical contact between TiO2 porous layer and PDMBI layer. The quasi-solid state cell efficiency fabricated with PDMBI as electrolyte was 2.26%. Furthermore, our device architecture is performing well because of the good band alignment among TiO2, dye, and PDMBI. In this research, we have successfully demonstrated gel-state and quasi-solid state dye-sensitized solar cells comprising PDMBI as electrolyte.