The three-dimensional mesoporous calcium oxide (meso-CaO) supported chromium-vanadium binary oxide catalysts yCrO(x)/10 wt.% VO(x)/meso-CaO (i.e., yCr/10V/meso-CaO, y=0-4 wt.%; the VO(x) and CrO(x) weight percentages referred to the mass contents of V(2)O(5) and Cr(2)O(3) in the catalysts, respectively) were prepared via an incipient wetness impregnation route and characterized by means of XRD, BET, SEM, TEM/SAED (selected-area electron diffraction), Raman, and H(2)-TPR (temperature-programmed reduction) techniques. The catalytic performance of the materials was evaluated for the oxidative dehydrogenation (ODH) of isobutane. It is found that the meso-CaO and yCr/10V/meso-CaO displayed wormhole-like mesoporous structures, VO(x) and/or CrO(x) were highly dispersed in the form of mono- and polyvanadate or polychromate on the surface of the meso-CaO support. The H(2)-TPR results indicate that 2Cr/10V/meso-CaO exhibited the best low-temperature reducibility among the as-prepared catalysts. Under the conditions of isobutane/oxygen molar ratio = 1/2, space velocity = 30,000 mL/(g h), and temperature = 540 degrees C, a maximal C(4)-olefins yield of 15% with the corresponding C(4)-olefins selectivity of 79% was achieved over the 2Cr/10V/meso-CaO catalyst. It is concluded that the good dispersion of CrO(x) and VO(x) domains and low-temperature reducibility of the catalyst as well as the strong basicity and three-dimensional wormhole-like mesoporosity of the CaO support were responsible for the excellent catalytic performance of 2Cr/10V/meso-CaO for the ODH of isobutane. (C) 2010 Elsevier B. V. All rights reserved.