The partial oxidation of propane has been compared on Fe/SiO2 and alkali-modified Fe/SiO2 catalysts. Addition of K+ to the catalyst can appreciably enhance the conversion of propane along with a high selectivity toward oxygenates. Adjacency of Fe and K on the silica surface seems to be important for the high oxygenate yield. Through the study on the reaction pathways, two types of intermediates, one derived from propene and the other from propan-2-ol, were postulated. The former is related to the acrolein formation and the latter to the acetone formation. Contribution of alkali-catalyzed aldol condensation is also discussed for the formation of oxygenates with higher carbon numbers.