A new polyoxovanadate compound [Co(pIM)V₂O₆] (1) was hydrothermally synthesized, where pIM stands for 2-(2-pyridyl)imidazole. For its characterizations, an integration of X-ray single crystal diffraction, powder X-ray diffraction, Fourier transform infrared spectra, and elemental analysis was accomplished. The compound exhibited a 2D architecture composed of VO₄ tetrahedra and CoO₃N₂ square pyramids via both edge - and corner - sharing. Considering the excellent catalytic oxidation features of polyoxovanadate, compound 1 was used as an efficient heterogeneous catalyst for the epoxidation of olefins with H₂O₂ as an oxidant, and could be reused without consuming activity. Besides, the magnetic studies indicated the antiferromagnetic interactions in 1.