The catalytic performance of MoBiTeO/SiO2 for selective oxidation of propane to acrolein was investigated, and the catalyst was characterized by means of X-ray powder diffraction, in-situ laser Raman spectroscopy, in-situ laser Raman spectroscopy, and X-ray photoelectron spectroscopy. The results showed that Te-polymolybdate species were the main active phase on the fresh catalyst. Under the conditions of 570 degrees C and C3H8/O-2/N-2 = 1.2/1/4, some Te species in the catalyst were reduced to metal Te which was volatilized during the reaction, and therefore the active surface phase of the catalyst was reconstructed, leading to the formation of MoO3 species. Along with the active surface reconstruction, both the conversion of propane and the selectivity for acrolein were increased, which was attributed to the synergistic effect between Te-polymolybdate and MoO3