Abstract VSiβ catalysts of V content varying between 0.14 and 4.0 V atoms/u.c., and containing VO x species of different coordination as shown by UV–vis spectroscopy, have been tested in oxidative dehydrogenation of propane. The catalytic performance depends on the V content, which controls the type of the VO x species. The catalyst of the lowest V content (0.14 V atoms/u.c.), in which isolated VO 4 tetrahedra are observed, is active but not selective, the only reaction product being CO 2 . At higher V content up to 1.22 V atoms/u.c., propene appears in the reaction products, its selectivity increasing with the V content, i.e. with the increase in the amount of tetrahedral species up to 1.22 V atoms/u.c. At still higher V content, at which octahedral V species appear, the selectivity to propene decreases. C 3 H 8 TPR measurements have shown that ODH of propane to propene may take place with the participation of the catalyst lattice oxygen, whereas this form of oxygen is not active in total combustion of the alkane.