In this paper, we demonstrated a new convenient route for in situ fabrication of well separated small sized WO3 nanoparticles in silica spheres, through a predeposition of surfactant encapsulated polyoxotungates as tungsten source, and followed by a calcination process. In a typical procedure, selected polyoxotungates with different charges were enwrapped with dioctadecyldimethylammonium cations through electrostatic interaction Elemental analysis, thermogravimetric analysis, and spectral characterization confirmed the formation of prepared complexes with the anticipated chemical structure The complexes were then phase-transferred into aqueous solution that predissolved surfactant cetyltrimethylammonium bromide, and finally incorporated into silica spheres through a joint sol-gel reaction with tetraethyl orthosilicate in a well dispersed state under the protection of organic layer for polyoxotungates from the alkaline reaction condition Transmission electron microscopic images illustrated the well dispersed WO3 nanoparticles in the size range of ca 2 2 nm in the silica spheres after the calcination at 465 degrees C. The sizes of both the silica spheres and WO3 nanoparticles could be adjusted independently through changing the doping content to a large extent Meanwhile, the doped polyoxotungate complexes acted as the template for the mesoporous structure in silica spheres after the calcination Along with the increase of doping content and surfactant, the mesopore size changed little (2 0-2.9 nm), but the specific surface areas increased quite a lot Importantly, the WO3-nanoparticle-doped silica spheres displayed an interesting photovoltaic property, which is favorable for the funtionalization of these nanomaterials.