Ordered ZnO nanowire arrays embedded in anodic aluminum oxide (AAO) membranes were fabricated by electrochemical deposition of Zn(NO3)2+H3BO3 solution in a boiling bath. Scanning electron microscope (SEM) and transmission electron microscope (TEM) observation results show that the polycrystalline ZnO nanowires with diameters around 100 nm were uniformly assembled into the ordered nanochannels of the AAO. The results of the investigation into photoluminescence (PL) and electronic paramagnetic resonance (EPR) measurements reveal that the interfaces between the ZnO nanowires and the pore walls of the AAO create a lot of oxygen vacancies, which are responsible for the green light emission (peaking around 512 nm) and the huge enhancement of the PL emission.