X-ray diffractometer, field emission scanning electron microscope (SEM, Hitachi S-4800), laser confocal micro-region Raman spectrometer and vibration sample magnetometer were used to systematically study the effects of polyethyleneimine concentrations and exposure time on the morphology and size of ZnO nanowire arrays. The photoelectric property and the relationship between the morphology of nanowire arrays and ferromagnetism at room temperature were also analyzed. Under 15 min exposure time, when the polyethyleneimine concentration is 2.25 g / L, the obtained ZnO nanowire array film exhibits the smallest size, the optimal density and vertical orientation. According to the study of luminescence and room temperature magnetism, it is shown that the optical and ferromagnetic property are related to the variation tendency of oxygen defects and surface defects of the ZnO nanowires.