Transient reaction at 273 and 300 K was used to study the initial steps in the photocatalytic oxidation (PCO) of benzene, toluene, p-xylene, mesitylene, benzyl alcohol, benzaldehyde, and m-cresol adsorbed on a thin film of TiO2 catalyst. Adsorbed aromatics were oxidized by O-2 photocatalytically in the absence of gas-phase aromatics, and the compounds remaining on the surface were characterized by temperature-programmed oxidation and desorption (TPO, TPD). Benzene and methyl benzenes oxidize rapidly at 273 or 300 K to form adsorbed intermediates that are more strongly adsorbed and much less reactive than the original aromatic, which is relatively weakly adsorbed on TiO2. The catalyst is expected to be covered with these intermediates during steady-state reaction. The rates of PCO of benzene and methyl benzenes to CO2 are slow relative to complete oxidation of alcohols or chlorinated hydrocarbons. The intermediates do not appear to be alcohols or aldehydes formed by oxidation of a methyl group, nor do they correspond to addition of an hydroxyl to the aromatic ring. Benzyl alcohol oxidizes photocatalytically to benzaldehyde and then to CO2 and H2O during PCO, but adsorbed m-cresol does not photocatalytically oxidize.