A combination of time-resolved techniques (part I) with kinetic isotope effects studies (part II) has been used to investigate the mechanism of the decatungstate (W10O324-) photocatalyzed oxidation of aromatic alcohols, in acetonitrile. It is demonstrated that aromatic alcohols exclusively react by hydrogen atom transfer (HAT) mechanism, like to that proposed for the analogous alkane oxidations, and not by an electron transfer (ET) which is predominant in alkenes. The primary and beta-secondary isotope effects provide strong evidence for a stepwise mechanism, in which the hydrogen atom abstraction occurs in the rate-determining step of the reaction. The positive slope in Hammett kinetics suggests a radical intermediate for this reaction and supports an early transition state. (c) 2006 Elsevier B.V. All rights reserved.