Oxidation dynamics of propene (CH3CH=CH2) to acrolein (CH2=CHCHO) on the anionic vanadium oxide cluster V4O11- is investigated with the first-principle density functional calculations, providing an interpretation to V4O11- + propene -> V4O10H2- + C3H6O observed in the photochemical reactions (Li, S.; Mirabal, A.; Demuth, J.; Waste, L.; Siebert, T. J. Am. Chem. Soc. 2008, 130, 16832). The complicated energy surface of the reaction between V4011- and propene is explored, and the stepwise dynamic processes for propene to acrolein are proposed. Initially, propene is captured by V4O11- with a hydrogen bond CH (methyl group in propene)center dot center dot center dot O (dioxo group in V4O11-), then undergoes dehydrogenation along this hydrogen bond to form a pi-allyl radical. After the redehydrogenation of the pi-allyl and oxygen transfer from the vanadium oxide cluster, acrolein is eventually produced together with four isomers of V4O10H2- in the different reaction paths. During this process, the negative charge is found to transfer between the hydrocarbon and the vanadium oxide moieties.