The possibility of using vanadyl phosphate (VOP)-based catalysts in biodiesel production has been investigated. Vanadium phosphate catalysts resulted very active in the transesterification reaction of triglycerides with methanol, despite their low specific surface area. A slow deactivation of the catalysts has been experimentally detected under the reaction conditions, but the catalyst can easily be regenerated by calcinations in air. The influence of the calcination treatment on the surface structure and, consequently, on its catalytic performances was deeply investigated. Both fresh and used catalysts were characterized by using several techniques, such as BET, X-ray diffraction (XRD), UV-vis diffuse reflectance (DRUV) and laser-Raman (LRS). The characterization results showed that the deactivation is due to a progressive reduction of vanadium (V) species from V5+ to V4+ and V3+ by methanol. By comparing the obtained performances of VOP catalysts with the ones of other heterogeneous catalysts reported by the literature, it is possible to conclude that VOP catalysts can already be used industrially for biodiesel production but their performances can probably be greatly improved in perspective. © 2006 Elsevier B.V. All rights reserved.