Water-soluble aluminum-coordinated polyoxotungstates, Cs-4[alpha-PW11{Al(OH2)}O-39]center dot 8H(2)O (Cs-1), [(CH3)(4)N](4)[alpha-PW11{Al(OH2)}O-39]center dot 8H(2)O (TMA-1), K6Na[(A-PW9O34)(2){W(OH)(OH2)}{Al(OH)(OH2)}{Al(mu-OH)(OH2)(2)}(2)]center dot 19H(2)O (KNa-2), and K-7[alpha(2)-P2W17{Al(OH2)}O-61]center dot 14H(2)O (K-3), were used as homogeneous catalysts or catalyst precursors for the oxidation of alcohols with 1 atm molecular oxygen in a water-alcohol biphasic medium. The catalytic activities and the stabilities of polyoxoanions were significantly affected by the structures around the aluminum sites constructed in the polyoxotungstates. In particular, polyoxoanion 1 exhibited high turnover numbers and high selectivities of the corresponding carbonyl products, and the molecular structure of 1 was remarkably stable for oxidations with long time intervals. (c) 2012 Elsevier B.V. All rights reserved.