Several amphiphilic polyoxometalate (POM) mesostructures are constructed that not only exhibit enhanced catalytic efficiencies for oxidation of sulfides but also provide easy and fast catalyst recovery from the reaction system. These amphiphilic POM building blocks show interesting self-assembly behavior at room temperature, and uniform POM-based nanowires and nanotubes are obtained, the structures of which depend greatly on the lengths of the alkyl chains in the surfactants.