The SO42--Fe-V/ZrO2 composite material was prepared by impregnation and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and N-2 adsorption-desorption to determine the phase composition and structural properties of the material. The results indicated that the SO42- species and V2O5 and Fe-2(V4O13) nanoparticles were supported on the ZrO2 support. The prepared composite was used as a catalyst for solvent-free oxidation of styrene into benzaldehyde using H2O2 aqueous solution as an oxidant, and it exhibited high activity and selectivity. The active sites on the catalyst surface were determined by exploring the relation between the phase composition and the catalytic activity. The effect of preparation conditions of the composite and reaction conditions on the catalytic performance was discussed. Besides, the reusability of the catalyst and the reaction mechanism were explored and proposed in this paper.