In-depth understanding of the kinetics of the vapor deposition process is substantial for advancing this capable bottom-up nanostructure synthesis approach into a versatile large-scale nanomanufacturing technology. In this paper, we report a systematic study of the vapor deposition kinetics of ZnO nanomaterials under controlled atmosphere and properly refined deposition conditions. The experiments clearly evidenced the self-catalyzed growth of ZnO NWs via the formation of ZnO nanoflowers. This result illustrated how ZnO morphologies were associated with the discrepancy between oxidation rate and condensation rate of Zn. The capability of switching the NW morphologies and possibly mechanisms was demonstrated by kinetically controlling the deposition system. The high Zn composition during the deposition resulted in strongly luminescent NWs, which can be used for optical imaging applications. This research discovered a fundamental kinetics that governs the mechanisms and morphology selection of nanostructures in a non-catalyst growth system.