This review summarizes published data on catalytic performances of different vanadium-containing oxides, including unsupported and supported V2O5, vanadates, solid solutions and mixed phases, in the oxidative dehydrogenation of C-2-C-5 alkanes. The analysis of the structure-activity relationships shows that various species characterized by a different reactivity exist on the surface of these catalysts. There are some indications that tetrahedral vanadium species are the most favourable for alkane oxidehydrogenation, Its intrinsic activity seems to be largely dependent on the structure of the nearest surrounding and, therefore, can be modified by changing the nature and number of the neighbouring ions. Although the reaction mechanism is generally accepted to be through the redox cycle between V5+ and V4+, opposite relationships between catalyst activity/selectivity and reducibility have been established, even for the same catalytic systems. No clear interpretation regarding the mode of alkane activation can be derived from a survey of the literature. This and some other aspects of the reaction mechanism need further studies at a molecular level.