In order to obtain a useful expression for the kinetics of the photocatalyzed total oxidation reaction of alkanes with oxygen and TiO2 as the catalyst, the dependence of the reaction rate on the concentration of the starting material species, the absorbed irradiation intensity, the wavelength of the light and the temperature was investigated. ne experiments were performed in a CSTR system. The rate law found for alkane oxidation differs from that obtained for olefin oxidation due to a different reaction mechanism. While a reversible catalyst deactivation process takes place in the latter case, there is no hint of such a process during alkane oxidation. The kinetic data lead to the conclusion that the formation of an alkane and a hydrogen-radical at a defect site of the catalyst is the first step in the total oxidation reaction of these species followed by the formation of a stronger adsorbed hydroperoxide species. The subsequent transformation of the hydroperoxide into further oxidized species mediated by the electron-hole pairs generated by the absorbed light on the semiconductor's surface was recognized to be the rate determining step. The reaction behavior for the investigated alkanes could be modeled using this concept with the exception of methane. Its rate law differs strongly from that found for ethane, propane as well as iso-butane.