Hollow ZnSnO₃ microspheres were successfully prepared by hydrothermal method at 160 °C for 12 h. The prepared material was characterized by field emission scanning electron microscope (FESEM), transmission electron microscope (TEM) and X-ray diffraction measurements (XRD). The average diameter of the hollow ZnSnO₃ microspheres was in the range of 400–600 nm. Compared with solid ZnSnO₃microspheres structure, the hollow ZnSnO₃ microspheres showed better response (S) to butane. To 500 ppm butane, the sensor response (S) of the hollow ZnSnO₃ microspheres was 5.79 at the optimum operating temperature of 380 °C, and the response and recovery time were 0.3 s and 0.65 s, respectively. The sensitivities of sensors based on this material were linear with the concentration of butane in the range of 100–1000 ppm.