The reaction pathways for selective oxidation of propane to acrolein on Ce0.1Ag0.3Mo0.5P0.3Ox Catalyst were investigated by three methods, (i) steady-state reaction test of the individual oxidation of propane and the probe molecule of possible reaction intermediates, (ii) temperature-programmed surface reaction (TPSR) study of propane oxidation in presence of gas phase O-2 or not, and (iii) in situ Raman spectroscopy investigation of propane oxidation and propylene oxidation on the catalyst. Based on the obtained results, three possible reaction pathways for selective oxidation of propane to acrolein on the catalysts are proposed. The major reaction pathway is that propylene (pi-allyl species) is produced from the activation of the methylene C-H bond of propane and further oxidizes to acrolein through or-allyl species. However, the presence of gas phase O-2 favors the formation of acrolein in propane oxidation on the catalyst. (C) 2008 Elsevier B.V. All rights reserved.