ZnO nanoparticles (NPs) containing H3PW12O40 polyoxometalates (POMs) were firstly synthesized by a simple solvothermal route. The photoanodes of dye-sensitized solar cells (DSSCs) were assembled with the as-prepared ZnO powder containing H3PW12O40. A comparative experiment in the absence of POMs was carried out to investigate the influence of H3PW12O40. Furthermore, the effects of other Keggin-type POMs including W series, Mo series, and the potassium salt K3PW12O40 were studied and different concentrations of H3PW12O40 were utilized to investigate the impact on the performance of DSSCs on the basis of the above research. The results demonstrate that the W-containing POM series HxMW12O40 (M = P, x = 3; M = Si, Ge, x = 4) significantly enhances the performance of DSSCs by increasing electronic lifetimes and reducing dark currents. The overall solar-to-electric energy conversion efficiency reached a maximum of 2.70 % in the presence of H3PW12O40, which is an improvement of 49.2 % compared to the efficiency without H3PW12O40. A suitable H3PW12O40 concentration is crucial.