Using synchrotron-based x-ray magnetic spectroscopy, we report a study focusing on the local symmetry of Cu-dopant and resultant structural imperfections in mediating Cu-doped ZnO nanoparticles' ferromagnetism (FM). Prepared by an antisolvent method, Cu appeared to preferably populate on the basal plane of ZnO with a local symmetry of [CuO4]. This unique symmetry was antiferromagnetic in nature, while electronically and structurally coupled to surrounded oxygen vacancies (Vo) that yielded a localized FM, because of a strong dependency on the number/location of the [CuO 4] symmetry. Surprisingly, the FM of undoped but oxygen-deficient ZnO appeared to be more itinerant and long-range, where Vo percolated the FM effectively and isotropically through oxygen's delocalized orbital. By adopting the approach of structural imperfection, this study clearly identifies Vo's (defect's) true characters in mediating the FM of magnetic semiconductors which has been thought of as a long-standing debate, and thus provides a different thinking about the traditional extrinsic ferromagnetic-tuning in the semiconductors. It even illuminates recent research concerning the intrinsic FM of low-dimensional systems that contain defects but non-magnetic elements.