The FeVxOy, catalysts, used for selective oxidation of propane to propylene and CO, were prepared via sol-gel method using F-127 as chelating agent. And the catalyst with V/Fe (molar ratio) = 0.1 showed quite good selectivity of propylene and CO and the sum of them can be more than 90%. The catalysts were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Raman, H-2-TPR and NH3-TPD. The relationship between the structure and catalytic properties was also preliminarily discussed. The results indicated that chemical interaction took place between the vanadium and iron, which could be referred to V-O-Fe bonds and the formation of Fe(VO4). Meanwhile, with the increase of vanadium content, the distribution of all the elements proportion and valence state on the surface of the catalysts as well as the acid amount and acid sites changed immensely. All of these affected the catalytic performance and improve the selectivity of CO and inhibit that of CO2. (C) 2014 Elsevier B.V. All rights reserved.