Vanadium substituted mesoporous AlPO have been synthesised using structure-directing surfactant under hydrothermal synthesis conditions. The presence of V in the framework of AlPO has been established by ESR, XPS, UV-vis DRS and ICP-AES measurements. This system is capable of promoting the oxidation of toluene to aldehyde and benzoic acid when the oxidising agent is 70% tert-butyl hydroperoxide while with 30% H2O2 cresols are formed. The activity of V-AlPO has been compared with those obtained with other similar porous materials like V-MCM 48, V-MCM-41, V-Al-Beta and VS-1. © 2004 Elsevier B.V. All rights reserved.