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ZnMoO 4 single crystals of high optical quality were grown using low temperature gradient Czochralski technique and their luminescence properties were studied. At low temperatures two overlapping luminescence bands with the maxima 1.93eV and 2.45eV were detected at E ex >3.9eV. The bands are attributed to the radiative recombination of self-trapped excitons of MoO42- parentage. High-intensity non-elementary peak of thermostimulated luminescence (TSL) observed at 65K is due to the thermal release of self-trapped holes. The threshold of TSL excitation spectrum at 6.2eV exceeds the bandgap value by 1.9eV and corresponds to electronic transitions from the valence band to the upper subband of the conduction band.