The conversion of propane in the presence of oxygen on V–K/Al2O3 catalysts with different surface area and in different feed conditions has been investigated. The activation energy measured at low conversion is 21kcal/mol (88kJ/mol) and the reaction order of propane is 1. In order to propose a reaction pathway, complementary experiments have been performed with a K-free V/Al2O3 catalyst, and propene and 2-propanol oxidation tests have also been done. A reaction scheme for the propane oxidation process is proposed. Two different reaction regimes have been observed. Below 950K true catalytic reaction occurs with propene, ethene, CO2 and CO as the only detectable products. Both COx and ethene productions likely occur through a parallel-successive reaction scheme with respect to propene production. The key surface intermediate is thought to be the sec-propoxide species, that can give propene by elimination and either COx or ethene by oxidation. Above near 950K a new regime involving gas-phase species is observed. In this range, where consumption of oxygen is already total or nearly total, the cracking of propane to ethene+methane becomes predominant. This reaction can be limited by filling the empty space of the reactor.