Metal-organic frameworks (MOF) of MIL-125 and NH2-MIL-125 have been successfully coupled with TiO2 nanotube array through a solvothermal method. MIL-125 and NH2-MIL-125 demonstrated notably high surface area. MOF/TiO2 heterojunctions can promote the separation of photo-generated e(-) /h(+) pairs during the photocatalytic process. Thus both MIL125 and NH2-MIL-125 modified TiO2 nanotube array showed enhanced photocatalytic activity under UV light. Under visible and solar light, NH2-MIL-125/TiO2 nanotube array demonstrated the highest photocatalytic response. The reason should be the red shift of optical absorption edge for the narrowed band gap of NH2-MIL-125.