Dye-sensitized solar cells (DSSCs) provide a promising alternative to traditional solar technologies, as they offer a unique mix of cost-effectiveness, adaptability, and the possibility of achieving high efficiency. This study aims to investigate the effect of SiO2 purity obtained from coal fly ash on the photoelectric performance of DSSCs. The study focuses on varying the purity of extracted SiO2 from coal fly ash as a counter-electrode material and examining its impact on the efficiency of DSSCs. The efficiency of DSSCs was assessed by evaluating the performance of several various SiO2 purity materials for counter-electrode materials. The performance testing of DSSCs revealed that the counter electrode material, consisting of artificial SiO2 with a purity of 99.9%, achieved the highest efficiency of 0.0113%. Subsequently, DSSCs were fabricated using counter-electrode materials derived from coal fly ash with a purity of 52.91%. These DSSCs demonstrated an efficiency of 0.0076%. DSSCs utilizing SiO2 with a purity of 91.20% exhibited an efficiency of 0.0062%. Dye-sensitized solar cells utilizing a counter electrode material composed of SiO2 with a purity level of 72.54% demonstrated an efficiency of 0.0061%. The results showed that the level of SiO2 purity obtained from coal fly ash has a substantial impact on the photoelectric performance of DSSCs, since higher purity of SiO2 is associated with improved efficiency.