In recent research in clean energy applications, clay has gained significant interest, especially as a gelator in dye-sensitized solar cells (DSSCs), for its capability to resolve the leakage issue of liquid electrolyte. In this paper, anionic hydrotalcite is utilized as a gelator to assist the formation of gel electrolyte in DSSCs. Three types of hydrotalcite with exchangeable anions, viz. NO3- (CL-N), CO32- (CL-C) and SO42- (CL-S), were synthesized with similar morphologies via the co-precipitation method. It is observed that the gel formation of hydrotalcite strongly depends on the exchangeable anions present in the hydrotalcite. The objective of this work is to understand the effect of hydrotalcite anions on the photovoltage and the photocurrent in the gel electrolyte through electrochemical analysis. With increasing ion affinity, the V-oc increases. This is attributed to Li+ intercalation with hydrotalcite compound resulting in the elevation of the conduction band of TiO2. With increasing ion affinity, the J(sc) decreases. This is attributed to the decreasing diffusion coefficient of triiodide and the increasing difficulty in the injection process. For anions with low ion affinity in hydrotalcite, the diffusion of the redox couple is not significantly affected by the high viscosity of the gel. Furthermore, the study indicates that proper selection of hydrotalcite compounds not only produces a quasi-solid gel electrolyte, but also increases the efficiency of the solar cells: the device performance was improved from 7.8% (liquid electrolyte) to 8.4% (hydrotalcite gel electrolyte).