In the present work, ZnO hierarchical microspheres were synthesized by hydrothermal methods in the sodium dodecyl sulfate-N,N-dimethyl-formamide-thiourea (SDS-DMF-thiourea) system. XRD, SEM, TEM, and N 2 adsorption measurements were used to characterize the prepared ZnO materials. Compared with ZnO nanoparticles (ZnO NPs), the as-prepared ZnO hierarchical microspheres (ZnO HMs) exhibit a better cataluminescence (CTL) response to ethanol. The response and recovery time of the home-made ethanol gas sensor with zinc oxide hierarchical microspheres as sensing materials were about 5s and 25s, respectively. The linear dependence of the sensitivity on the ethanol concentration was observed in the range of 4–400ppm with excellent selectivity. These results indicated that ZnO hierarchical microspheres would be a good candidate for fabricating practical cataluminescence ethanol sensor.