A series of CuO–V2O5/Al2O3 catalysts were prepared and characterized by various techniques such as XRF, BET, XPS and XRD. These catalysts were used for liquid-phase amination of toluene to toluidines. It was found that adding copper species to V2O5/Al2O3 catalyst showed a peculiar behavior, maintaining a high activity toward toluene amination. An optimum CuO content appeared at 1.6 wt% with a CuO/V2O5 molar ratio of 0.25. More than 60% total yield of toluidines was obtained over 1.6%CuO–15%V2O5/Al2O3 catalyst under optimized conditions. Catalyst characterizations revealed that the addition of copper improved the formation of V5+ species, thus enhancing the activity of the catalyst.