The ammoxidation of substituted toluenes to their corresponding nitriles over silica|supported vanadium phosphorus oxide (VPO/SiO 2 ) catalysts has been studied. The effects of carrier silica, the addition of phosphorus, the substituents and the loadings have been discussed. Compared with unsupported VPO, the VPO/SiO 2 catalysts have higher catalytic activity for ammoxidation of substituted toluenes and much lower reaction temperature. XRD shows that vanadium phosphorus oxides exist as amorphous phase and disperse to a high degree on the silica surface in 10 % loading catalyst. When the loadings are over 10 %, the crystalline α |VOPO 4 would emerge, which would decrease the yield and selectivity. Additional phosphorus can form composite oxides with vanadia and play concerted catalytic function, which increase the selectivity of nitriles remarkably. Different substituents or same substituents on diffetent positions have different influences because of the variant electronic stability of intermediates, the hindered accessibility of methyl group or the chemisorption state of the substrate molecule on the electrophilic catalyst surface. The ammoxidation of substituted toluenes to their corresponding nitriles over silica | supported vanadium phosphorus oxide (VPO / SiO 2) catalysts has been studied. The effects of carrier silica, the addition of phosphorus, the substituents and the loadings have been discussed. with unsupported VPO, the VPO / SiO 2 catalysts have higher catalytic activity for ammoxidation of substituted toluenes and much lower reaction temperature. XRD shows that vanadium phosphorus oxides exist as amorphous phase and disperse to a high degree on the silica surface in 10% loading catalyst When the loadings are over 10%, the crystalline α | VOPO 4 would emerge, which would decrease the yield and selectivity. Additional phosphorus can form composite oxides with vanadia and play concerted catalytic function, which increase the selectivity of nitriles remarkably. Different substituents or same substituents on diffetent positions have different influences because of the variant e lectronic stability of intermediates, the hindered accessibility of methyl groups or the chemisorption state of the substrate molecule on the electrophilic catalyst surface.