A series of vanadyl pyrophosphate catalyst (VPO) modified by different additives have been prepared with the aim to study the performance for selective conversion of n-butane to maleic anhydride(MA). The addition of various promoters improved the catalytic performance remarkably on both activity and selectivity. The correlation of activity and selectivity of the catalysts with their structure has been discussed. The increase in BET surface areas and surface redox sites leads to an enhanced activity. However,good selectivity can only be obtained on those surfaces with suitable surface acid sites.