Single crystalline Zn2SnO4 (ZTO) nanorods 2-4 nm in diameter and around 20 nm in length were successfully synthesized by a simple hydrothermal process with use of hydrazine hydrate as an alkaline mineralizer instead of NaOH or NH3 center dot H2O. By analyzing the UV-vis diffuse reflectance spectrum, the optical band gap (E-g) of the nanorods was found to be 3.87 eV, which indicates a blue shift of 0.27 eV from that of bulk ZTO (3.6 eV). In situ high-temperature X-ray diffraction was employed to study the thermal expansion coefficient and the variation of lattice parameter with temperature of the product. Furthermore, we discussed the chemical mechanism and key factors to the hydrothermal formation of the sub-5 nm ZTO nanorods.