Through loading of TiO₂ on the surface of K₆SiW₁₁O₃₉Co(II)(H₂O)·xH₂O (SiW₁₁Co), a novel photoanode material has been created for dye-sensitized solar cells (DSSC). The absorbing band as well as photoelectricity response range of TiO₂@SiW₁₁Co is extended to the visible range. In addition, the absorption in the UV range is enhanced notably compared with P25 (raw TiO₂). More importantly, the recombination of the TiO₂ network is avoided. TiO₂@SiW₁₁Co is mixed with P25 powder (wt ∼1 : 1) to assemble dye-sensitized (N719) solar cells, which exhibit a short-circuit photocurrent density as high as 18.05 mA cm⁻², which is 64% higher than blank samples under the standard AM1.5G global solar irradiation. In addition, the mechanisms for SiW₁₁Co in DSSC are proposed.