Nano-sized Zn2SnO4 materials have been synthesized using the coprecipitation method. The synthetic conditions and the calcination behaviors of nano-sized Zn2SnO4 materials have been studied. The nano-sized Zn2SnO4 materials have been characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetry and differential thermal analysis (TG-DTA) and specific surface area. As a result, the kinetic grain growth equation for nano-sized Zn2SnO4 can be expressed as D4.78 = 9.12 × 1023t exp(−40.6 × 103/T), with an activation energy for grain growth of Q = 337.9 KJ/mol. The nano-sized Zn2SnO4 materials have been used as photocatalysts to decompose benzene in water solution. The results show that Zn2SnO4 can photocatalytically decompose benzene, and the photocatalytic capacity for Zn2SnO4 relates to the grain size, which is discussed in terms of the surface effect and the quantum size effect.