A series of vanadium phosphorus oxides (VPO) were prepared by using dodecyl amine as surfactant and tested for the partial oxidation of isobutane and isobutene. Characterization results showed that their structure and properties depend on the content of dodecyl amine. Catalytic tests showed that relatively high isobutane conversion and desired product selectivity can be achieved over a proper dodecyl amine doping VPO catalyst. It is also found that higher isobutane conversion can be achieved over V4+-containing phases as compared to V5+-containing phases, while proper surface V5+/V4+ ratio may be propitious to obtain high selectivity to methacrylic acid for the selective oxidation of isobutane. In addition, the content of dodecyl amine in the preparation of the VPO catalysts appears to be more important in determining the surface P/V ratio of the catalysts.