A new oxidovanadium (IV) Schiff base complex, VOL2 (1), containing furfuryl pendant group was synthesized by the reaction of the related bidentate O, N-type Schiff base ligand and VO(acac)2 in the ratio of 2:1 in methanol in the reflux conditions. The Schiff base ligand and its vanadyl complex were characterized by 1H-NMR and FT-IR spectra and elemental analysis. The crystal structure of 1was also determined the single-crystal X-ray analysis. It showed that the metal center located in a distorted tetragonal pyramidal (N2O3) geometry in which the two bidentate Schiff base ligands were coordinated to the vanadium (IV) ion in four equatorial positions, and one oxygen atom in its axial position. The catalytic activity of the vanadyl Schiff base complex was elucidated in the epoxidation of cyclooctene as a model substrate. Different reaction parameters were investigated in this reaction and the results showed that it was an effective and selective catalyst in these optimal conditions. Thermogravimetric analysis of 1 showed that it was decomposed in two stages by losing two methoxy groups and other organic residuals, respectively, in the temperature range of 253–532 oC. In addition, the vanadyl Schiff base complex (1) was thermally decomposed in air at 660 °C and the XRD pattern of the obtained solid showed the formation of the V2O5 nano-particles with the average size of 52 nm.