In this contribution, we address two critical and interesting aspects from both fundamental and technological point of views, which are the polarity of ZnO and the interface reactivity and stability to hydrogen and nitrogen. The effects of atomic hydrogen and nitrogen produced by radiofrequency (r.f. ,13.56 MHz) H2 and N2 plasmas and of temperature on the optical, compositional and structural properties of Zn- and O-polar ZnO have been studied. It is found that Zn-polar ZnO is highly reactive with atomic hydrogen while O-polar ZnO is almost inert. Conversely, both polarities react with nitrogen, with the O-polar ZnO showing a larger reactivity toward N-atoms than the Zn-polarity.