Artificial photosynthesis from CO2 reduction is severely hampered by the kinetically challenging multi-electron reaction process. Oxygen vacancies (Vo) with abundant localized electrons have great potential to overcome this limitation. However, surface Vo usually have low concentrations and are easily oxidized, causing them to lose their activities. For practical application of CO2 photoreduction, fabricating and enhancing the stability of Vo on semiconductors is indispensable. Here we report the first synthesis of ultrathin WO3 center dot 0.33H(2)O nanotubes with a large amount of exposed surface Vo sites, which can realize excellent and stable CO2 photoreduction to CH3COOH in pure water under solar light. The selectivity for acetum generation is up to 85%, with an average productivity of about 9.4 mu mol g(-1) h(-1). More importantly, Vo in the catalyst are sustainable, and their concentration was not decreased even after 60 h of reaction. Quantum chemical calculations and in situ DRIFT studies revealed that the main reaction pathway might be CO2 -> (COOH)-C-center dot -> (COOH)(2) -> CH3COOH.