A set of vanadium phosphorous oxide (VPO) catalysts, mainly consisting of (VO)(2)P2O7, VO(PO3)(2) or VOPO4.2H(2)O bulk crystalline phases, has been investigated for the oxidative dehydrogenation (ODH) of ethane to ethylene, a key potential reaction for a sustainable industrial and socioeconomic development. The catalytic performance on these VPO catalysts has been explained on the basis of the main crystalline phases and the corresponding surface features found by XPS and LEISS at 400 degrees C, i.e. within the temperature range used for ODH reaction. The catalysts based on (VO)(2)P2O7 phase presented the highest catalytic activity and productivity to ethylene. Nevertheless, the catalysts consisting of VO(PO3)(2) structure showed higher selectivity to ethylene, reaching 90% selectivity at ca. 10% ethane conversion. To the best of our knowledge, this is the highest selectivity reported on a vanadium phosphorous oxide at similar conversions for the ethane ODH. In general, catalysts consisting of crystalline phases with vanadium present as V4+, i.e. (VO)(2)P2O7 and VO(PO3)(2), were found to be significantly more selective to ethylene than those containing V3+ phases. The surface analysis by XPS showed an inverse correlation between the mean oxidation state of vanadium near surface and the selectivity to ethylene. The lower averaged oxidation states of vanadium appear to be favoured by the presence of V3+ species near the surface, which was only found in the catalysts containing V4+ phases. Among those catalysts the one based on VO(PO3)(2) phase shows the highest selectivity, which could be related to the most isolated scenario of V species (the lowest V content relative to P) found at the outermost surface by low energy ion scattering spectroscopy (LEISS), a "true" surface technique only sensitive to the outermost atomic layer. (C) 2017 Elsevier Inc. All rights reserved.