The high versatility of nanostructured ZnO has drawn considerable attention from the scientific community since the second half of the two thousand decade. Within this timeframe, electrospinning became one of the simplest ways to produce nanostructured ZnO. In this work, we present the production and characterization of ZnO nanoparticles obtained from electrospun fiber mats using the highest (1:2) PVOH/ZnAc proportion reported so far. The thermally annealed samples were characterized using, X-Ray Diffraction (XRD), High Resolution Scanning Electron Microscopy (HRSEM), Energy Dispersive X-Ray analysis (EDS) and Cathodoluminescence (CL). The results obtained show that all annealed samples present excess zinc as oxygen vacancies (V-O, V-O(+)) or oxygen antisites (O-Zn) which contribute to a considerable change in the CL spectra. This change evidences the presence of defect levels within the ZnO gap, which might be an indication that our nanoparticles present higher catalytic activity within the visible spectrum.