A tungstophosphate derivative, (Bu 4 N) 3 PW 11 O 39 [O(SiOH) 2 ] (TBAPW 11 Si 2 ), with Si-OH groups on the surface was grafted on mesoporous TiO 2 synthesized by an evaporation-induced self-assembly method. Such TBAPW 11 Si 2 /TiO 2 mesoporous hybrid materials were characterized by IR, XRD, N 2 adsorption-desorption, TEM and ICP-AES techniques. It was shown that the covalent linkage between TBAPW 11 Si 2 and TiO 2 formed by condensation of Si-OH on TBAPW 11 Si 2 with Ti-OH on TiO 2 . Enough Ti-OH groups on TiO 2 surface and the calcination at a certain temperature were necessary for the condensation. Compared with TiO 2 support, the hybrid samples had a little higher crystallinity of anatase, but the surface area, pore volume and pore size decreased as TBAPW 11 Si 2 loading increased. In the degradation of methyl orange, these hybrid samples exhibited higher photocatalytic activities than anatase TiO 2 support, and their activities were even comparable with that of Degussa P25 with much higher crystallinity, which can be mainly attributed to a synergistic effect between polyoxometalate and TiO 2 .