To elucidate the nature and states of the surface oxygen sites on SnO2 and the relationship between the surface vacancies and the active oxygen sites, a series of SnO2 samples have been fabricated by microwave/ultrasound and KCC-1 hard template. By adjusting the preparation methods, SnO2 samples with varied surface and texture properties were obtained, which display different intrinsic activities for toluene deep oxidation, following the sequence SnO2 -Ultra-OH > SnO2 -Stir-OH > SnO2 Mic > SnO2 -Pre. For the first time, it is discerned clearly with in situ diffuse reflectance infrared Fourier transform spectroscopy, X-ray photoelectron spectroscopy, and electron paramagnetic resonance techniques that both superoxide O(2)(- )and peroxide O-2(2-) anions are present on SnO2 surface as active oxygen species. Generally, these more active SnO2 samples possess richer surface active O-2(-), O-2(2-) anions and acidic sites. The concerted interaction between surface O-2, O-2(2-) anions and acidic sites is concluded to be the predominant reason determining the toluene total oxidation activity over SnO2.