VTeO/SiO2 catalyzed the oxidation of propane into acrolein with a maximal yield of 6.6% obtained at 520 degrees C. The catalytically active sites of the catalysts were investigated using propene and allyl bromide as molecular probes. The V5+ sites were responsible for oxidative dehydrogenation of propane, whereas the Te4+ sites for ce-H abstraction of propene and O-insertion of allyl species.