The defect structure of ZnO nanoparticles is characterized by means of high-field electron paramagnetic resonance (EPR) spectroscopy. Different point and complex defects could be identified, located at the "bulk" or the surface region of the nanoparticles. In particular, by exploiting the enhanced g-value resolution at a Larmor frequency of 406.4 GHz, it could be shown that the resonance commonly observed at g = 1.96 is comprised of several overlapping resonances from different defects. Based on the high-field EPR analysis, the development of a space-charge layer could be monitored that consists of (shallow) donor-type [Formula: see text] defects at the "bulk" and acceptor-type [Formula: see text] and complex [Formula: see text] defects at the surface. Application of a core-shell model allows to determine the thickness of the depletion layer to 1.0 nm for the here studied compounds [J.J. Schneider et al., Chem. Mater.22, 2203 (2010)].