V-doped TiO2 (V-TiO2) was synthesised using solvothermal technique and immobilised onto fibreglass cloth (FGC). The XRD pattern of doped sample showed slight positive shift to higher angle indicating that the V ions were well substituted into the Ti lattices. The band-gap energy of V-TiO2 was lower than that of P25, pure TiO2, (3.28 eV for P25 and 2.90 eV for V-TiO2) demonstrating it could be excited by visible light. The XANES spectra of the Ti K-edge transition indicated most Ti ions were in the tetravalent state with octahedral coordination. The A2 species on the surfaces of V-TiO2 were found to be the main active sites during photocatalytic degradation of BTEX under visible light irradiation.