Density functional B3LYP calculations have been employed to investigate the reaction of platinum oxide with methane. PtO is shown to form a molecular complex with CH 4 bound by ~13 kcal/mol. At elevated temperatures, direct abstraction of a hydrogen atom is possible leading to PtOH and free methyl radical with a barrier of ~26 kcal/mol. A minor reaction channel is insertion into a C-H bond to produce a CH 3 PtOH molecule, which can be also formed by recombination of PtOH and CH 3 . CH 3 PtOH would preferably dissociates through a mechanism involving 1,2-CH 3 migration to produce a PtCH 3 OH complex and eventually Pt+CH 3 OH.