The effect of silver (Ag) loading on titanium-supported vanadium (Ag-V/TiO2) catalysts, prepared by impregnation method, on the oxitative dealkylation behavior of 3-picoline has been investigated. At optimum loading of 2mol % Ag was found to enhance the catalytic performance in terms of yield (80.1%) and selectivity (84.7%). As evidenced by X-ray photoelectron spectroscopy (XPS) and H2 temperature-programmed reduction (H2-TPR), Ag is attributed to promotion of the formation of surfance oxygen species and change of the valence of vanadium species (V4 /V5 ) through interaction of V and Ag, shortened the time of reduction process, increased the oxidative activity. Additionally, Ag highly dispersed on the catalysts as atom, which could formed silver oxide (Agp O oxygen species: O-, O2- and O2-) by adosorbed the O2. Thus, the selective oxidation of methylarene were modified over the Ag-V/TiO2 catalysts, which pyridine as the main product was found with few nicotinic acid.An oxidative machnism was conjectured: C-H bond was activited by V4 /V5 (oxygen species: O2-) and Agp O absorbed on the C-C bond because of the O- and O2- were strong electrophilic reactants, which attacted the site of high charge density of reacted molecule, causing the C-C bond to decompose, -CH3 was oxidatived to form COx.