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Nano and micro crystalline ZnO were synthesized by two different sol-gel routes. The nominally undoped ZnO crystals were investigated by X-ray diffraction, electron paramagnetic resonance (EPR), photoluminescence (PL) and electron microscopy. These measurements are discussed together with surface and volume conductivity measured. Two intrinsic defects were observed having g factors close to that of the shallow donor in ZnO. A further defect was correlated with the conductivity of ZnO nanocrystals and is shown to be due to a surface-related defect. (© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [ABSTRACT FROM AUTHOR]