Structural and optical properties of ZnO nanoparticles can be fine tuned by a novel variant of milling performed at cryogenic temperatures. In this study intrinsic defect centers such as oxygen and zinc vacancies are characterized using electron paramagnetic resonance (EPR) and photoluminescence (PL) spectroscopy. Three different surface defects with different g factors were identified by EPR for which the spectral intensities change upon decreasing the crystal size. EPR and PL intensities revealed a linear correlation giving detailed information about optical and electronic properties of ZnO. The core-shell model established from optical emission and EPR suggests distinguished electronic states in the band gap belonging to negatively charged Zn vacancies and positively charged oxygen vacancies. This model indicates a correlation between red emission and positively charged oxygen vacancies, which lead to a possible transition from a typical n-type to a p-type ZnO semiconductor.