To explore the origin of magnetism, the effect of light Cu-doping on ferromagnetic and photoluminescence properties of ZnO nanocrystals was investigated. These Cu-doped ZnO nanocrystals were prepared using a facile solution method. The Cu2+ and Cu+ ions were incorporated into Zn sites, as revealed by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). At the Cu concentration of 0.25 at.%, the saturated magnetization reached the maximum and then decreased with increasing Cu concentration. With increasing Cu concentration, the photoluminescence (PL) spectroscopy indicated the distribution of VO+ and VO++ vacancies nearly unchanged. These results indicate that Cu ions can enhance the long-range ferromagnetic ordering at an ultralow concentration, but antiferromagnetic “Cu+-Vo-Cu2+” couples may also be generated, even at a very low Cu-doping concentration.