Methyl tert-butyl ether (MTBE) has been added into fuel extensively as oxygenate. Due to high water solubility, MTBE is not easy to be removed from contaminated groundwater. Common control techniques for MTBE include combustion, adsorption, biological treatment and air stripping etc. In this study, the V-doped TiO2 was synthesized by modified sol-gel method and its’ photocatalytic degradation effect on MTBE irradiated under visible (λ= 419 nm) was evaluated. The crystal structure of V-doped TiO2 was found mainly anatase using the X-ray diffractometer (XRD)and its size was estimated about 20 nm using field-emission scanning electron microscope (FE-SEM). According to the brunauer emmett teller (BET), the surface area of doped Vanaduium on TiO2 decreased due to the decrease of porodity. Comparing with the response for visible light, the V-TiO2 complex had significantly efficiency of photocatalytic degradation for MTBE under visible light irradiation and the destruction removal efficiency (DRE) of photocatalytic degradation was up to 83 % for 10 ppm of MTBE under visible light irradiation.These evidences suggest that the composite V-TiO2 under visible light irradiation can be widely used to treat other organic hazardous or recalcitrant pollutants in the practical contaminated groundwater.