Building an effective way for finding the role of surface defects in gas sensing property remains a big challenge. In the present work, we synthesized the ZnO nanodishes (NDs) and first explored the formation process of rich electron donor surface defects by means of studying mechanism for the ZnO NDs synthesis. The test results revealed that ZnO-6, added by 6 mmol Zn powder, had the best gas-sensing properties with the excellent selectivity to ethanol than the others. Specially, the ZnO-6 sensor exhibited the best response (about 49) to 100 ppm ethanol at 230 °C among four as-synthesized samples, while noncustomized ZnO was only 28. It was mainly caused by the following two reasons: the exposure of target (0001) crystal facet and rich electron donor surface defects zinc interstitial (Zn) and oxygen vacancy (V). As a guide, the formation process of surface defects was revealed by an ideal defect model. By the small-angle XRD and TEM patterns, we could conclude that ZnO NDs, changing stoichiometric ratio, increased the content of Zn by adding Zn powder, while excessive Zn powder promoted the growth of c axis of ZnO NDs in the self-assembly engineering. Besides, a depletion model has been provided to explain how the surface defects work on the sensors and the complex mechanism of gas sensing performance. These findings will develop the application of ZnO-based gas sensor in health and security.