In this work, we have demonstrated that amorphous ZnO nanobranches (a-ZnO NBs) could spontaneously react from the crystalline ZnO NWs (c-ZnO NWs) at specific humid environment. The spontaneous reaction mechanism and result can be analyzed by humidity controlling and optical microscope (OM)/scanning electron microscope (SEM)/Kelvin probe force microscopy (KPFM)/transmission electron microscopy (TEM) system. We can make the c-ZnO NWs spontaneous reaction happen at different humid environments and suppress the a-ZnO NBs spontaneous reaction by oxygen/hydrogen plasma surface passivation. The hydrogen plasma surface treatment also can improve the UV sensing sensitivity more than twofold. This work provides the mechanism and methods of the a-ZnO NBs spontaneous growth and offers the passivation treatment for strengthening and enhancing ZnO-based nanodevice application in humid environment and UV light detection, respectively.