The process of the oxidative dehydrogenation of butenes over a nickel-vanadium-antimony supported catalyst proceeds with a higher conversion and selectivity as compared to the dehydrogenation of n-butane. It was found that the maximum yield of divinyl per pass from the butylene fraction reaches 44% at a 68% selectivity. The maximum selectivity of the process (75%) is achieved at a divinyl yield of no more than 40%. The addition of nickel oxide to antimony vanadate results in the simultaneous formation of both nickel vanadate and antimonate, which are responsible for the conversion of butylenes to divinyl. Systems based on the supported Ni-V-Sb oxide matrix were analyzed with the use of the BET, X-ray photoelectron spectroscopy, diffuse reflection spectroscopy, X-ray diffraction, and hydrogen temperature-programmed reduction techniques. The formation of the NiV2O6 nickel vanadate phase results in the most selective catalyst with an increased amount of mobile oxygen in the lattice due to the presence of vanadium.