TiO2 immobilized on SiO2 (TiO2/SiO2) have been prepared by sol-gel method and various ions of transition metals (Cr3+, Co2+ Ni2+, CU2+, and Zn2+) were doped on the photocatalyst using wet impregnation method under reducing calcination atmosphere. The photocatalytic activity of metal doped TiO2/SiO2 towards phenol degradation under black light irradiation were investigated and compared with undoped TiO2/SiO2. The results showed that the photoresponse of Cu2+ and Zn2+ doped TiO2/SiO2 were larger than undoped TiO2/SiO2, indicating that the photogenerated carriers were separated more efficiently in Cu2+ and Zn2+ doped TiO2/SiO2. The reactivity was in the order of Cu2+ > Zn2+ > Ni2+ > Cr3+ > Co2+. The different photoreactivity was ascribed to combine effect of the different ionic radii and photocorrison tendency of the dopants. The sample was also characterized by surface analytical methods such as X-ray diffraction, scanning electron micrograph/electron dispersive X-ray analyzer and UV-Vis absorption spectrum.