The present invention provides a catalyst composition for the production of olefins by oxidative dehydrogenation of hydrocarbons, and of using such catalyst compositions. The catalysts of the present invention include compositions of the formula: X.sub.xY.sub.yWO.sub.z wherein X is at least one element selected from the group consisting of Li, Na, K, Rb, Cs, and Fr; Y is at least one element selected from the group consisting of B, Al, Ga, In, Ti, C, Si, Ge, Sn, and Pb; x is 0.5-2.5; y is 0.05-5; and z is the number of oxygen atoms required to satisfy the valancy of X, Y, and W in said composition. The methods and catalysts of the present invention are specifically useful for the combined production of propene and isobutene at relatively high conversion, selectivity, and productivity, and with minimal side products.