Size tunable solid SnO 2 (STO) and hollow SnO 2 (HTO) nanospheres were prepared by a sacrificing template method. The peaks around 390nm were observed in photoluminescence (PL) spectra. Based on the results, the PL intensity exhibits morphology-dependence and size-dependence, and HTO structure displays better optical properties than STO structure. The degradation of Methyl Orange (MO) in aqueous solution is selected as a probe reaction to evaluate the catalytic activity of nano-SnO 2 . The result shows that HTO structure presents stronger photocatalytic (PC) activity. According to the result of specific surface area testing, the improved PL and PC properties of HTO structure can be mainly explained by the surface effect induced by large specific surface area. This work is meaningful for developing nanomaterials with enhanced optical and photochemical properties.