Ethanol photo-oxidation was investigated over mesoporous, amorphous V+TiO2 and V+TiO2(anatase) catalysts. Under the UV + visible light, mesoporous V+TiO2 generally exhibited faster photo-oxidation rates than V+TiO2(anatase) catalysts did. VIV doping directed preferable formation of acetic acid rather than predominant acetaldehyde formation. Under the visible light only, mesoporous VIV-TiO2 catalyst exhibited best reactivity among all V+TiO2 catalysts. Ethanol dehydration reaction was preferred. Initial quicker water evolution may suggest greater oxidation capability compared to V+TiO2(anatase) catalysts.