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Selective photocatalytic oxidation of alcohols into value-added aldehydes or ketones is a promising alternative for alcohol oxidation concerning the mild reaction conditions and the controllable selectivity. To increase the activity, defective Bi2WO6 with abundant oxygen vacancies (OVs) was synthesized via substitution of W by Ta. The resulting Ta-doped Bi2WO6 loaded with Pt nanoparticles as co-catalyst efficiently converted aromatic and aliphatic alcohols into the corresponding carbonyl compounds with high selectivity (>99%) in aqueous solution under visible-light irradiation and anaerobic conditions, with equivalent H2 as a coupled product. The optimal amount of benzyl alcohol converted by the Ta-doped catalyst was two times higher than that of the undoped catalyst. Surface OVs were found to favor the dissociative adsorption of the alcohols and to prolong the life time of the charge carriers. More importantly, isotopic labelling experiments confirmed that over Pt-loaded pristine undoped Bi2WO6, the coupled H2 product results from water reduction, while over Pt-loaded Ta-doped Bi2WO6, the produced H2 originates from benzyl alcohol, implying that benzyl alcohol can be photo-oxidized via a complete dehydrogenation pathway. Thus, enriched surface OVs in photocatalysts can activate α-C-H bonds in alcohols, boosting the photocatalytic oxidation performance.