Monodisperse fullerene-like polyoxometalate-based microspheres are synthesized using a single-phase approach which is quick, easier to control surfactant to polyoxometalate (POM) molar ratios and result in better control over the size-distribution range. Noble-metal nanocrystals are successfully incorporated in the surfactant encapsulated complex multilayered spherical assemblies without any change in their layered morphology. Combining the merits of fullerene-like POMs and monodisperse noble metal nanocrystals, these monodisperse hybrid spheres show interesting composition- and size-dependent photochemical properties.