Novel growth morphologies of sharp needle-shaped tetrapods and coexistent tetrapods and nanowires of ZnO have been prepared by sublimation of pure Zn utilizing a simple solid – catalyst free - vapor mechanism at the temperatures of 950 and 1100 ºC respectively. These striking differences in these microscopic objects, which evolved at two different process temperatures, were deduced from electron paramagnetic resonance and Raman spectra thereby revealing the role of microstructures, defects and oxygen vacancies in ZnO at lattice scale, which are receptive for luminescence, and electrochemical activity of this functional oxide.