SnO2 hollow microspheres were fabricated via a hydrothermal synthesis method assisting by the complex surfactant system of polyacrylamide and polyethylene glycol.Observation by field emission scanning electron microscopy (FESEM) showed the SnO2 hollow spheres were composed of nanoparticles.The growth mechanism for the formation of hollow spheres was proposed.UV spectroscopy and photoluminescence (PL) were used to investigate the optical properties of the products.The PL result showed that four peaks,containing the emission from recombination of free excitons,were observed in the photoluminescence spectrum. SnO2 hollow microspheres were fabricated via a hydrothermal synthesis method assisting by the complex surfactant system of polyacrylamide and polyethylene glycol. Observe by field emission scanning electron microscopy (FESEM) showed the SnO2 hollow spheres were composed of nanoparticles. Growth mechanism for the formation of hollow spheres was proposed. UV spectroscopy and photoluminescence (PL) were used to investigate the optical properties of the products. PL result showed that four peaks, containing the emission from recombination of free excitons, were observed in the photoluminescence spectrum.