Three important elements of Zr, Mo and Zn were introduced into the VPO precursor derived in the aqueous medium, and the effects of the introduced elements on the physico chemical properties of the VPO base such as the surface area, phase composition and catalytic performance were studied accordingly. The modulated samples were also subject to further mechanical milling in order to change the surface state and particle size of the samples. It was found that both the combination of different additives and the mechanical milling would obviously affect surface area and morphology of the modulated samples. The added components and the mechanical milling reduced the complexity of the phase composition and increased the content of the (VO)2P2O7 phase. The combination of Mo and Zn components showed the best positive promotion effect and the following milling process can enhance this effect further. It was also found that the catalytic performance could also be improved somewhat by treating the catalyst at regular intervals with the fresh air during the reaction. Three important elements of Zr, Mo and Zn were introduced into the VPO precursor derived in the aqueous medium, and the effects of the introduced elements on the physico chemical properties of the VPO base such as the surface area, phase composition and catalytic performance were studied accordingly. The modulated samples were also subject to further mechanical milling in order to change the surface state and particle size of the samples. It was found that both combination of different additives and the mechanical milling would obviously affect surface area and morphology of the modulated samples. The added components and the mechanical milling reduced the complexity of the phase composition and increased the content of the (VO) 2P2O7 phase. The combination of Mo and Zn components showed the best positive promotion effect and the following milling process can enhance this effect further. It was also found that the catalytic performance could also be more aware by treating th e catalyst at regular intervals with the fresh air during the reaction.