Abstract The oxidation of three methyl-diphenylmethane isomers and of bibenzyl, benzyl alcohol, and benzaldehyde, which are intermediates in the catalytic oxidation of toluene over V 2O 5, has been studied to elucidate the reaction network and relative importance of various reactions. Selectivity dependences reveal that the network is composed mainly of three parallel reaction routes: (1) sidechain oxidation with consecutive reactions, (2) oxidative coupling with both parallel and consecutive reactions, and (3) carbon oxide formation. Coupling products are not negligible, with an initial selectivity of 29% (400°C). Anthraquinone is produced mainly from o-methyl-diphenylmethane through o-methyl-diphenylmethanone. Initial ring oxidation products were not found with the conditions and catalyst used. Selectivity depencences suggested product lumping and a simplified network. Kinetic analysis of this reaction network indicates that higher temperatures favor route 2 over route 1. The same initial intermediates for route 1 of side-chain oxidation and for route 2 of oxidative coupling are suggested.