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[Display omitted] • Electron and hole trapping centers were observed in the molybdenum doped zinc oxide rods. • Electron trapping centers were mostly molybdenum-based. • Holes were trapped at oxygen complexes. • Exciton- and defect-related emission bands appear suppressed after X-ray irradiation. • Zinc vacancies participated in the charge trapping processes. Peculiarities of the point defects creation under X-ray irradiation and the influence of Mo doping in ZnO powders of nano- and microrods fabricated by the hydrothermal growth method (as-grown and annealed in air) were studied in detail. Correlated experiments of X-ray diffraction, X-ray photoelectron spectroscopy, electron paramagnetic resonance, photo- and radioluminescence as well as thermally stimulated luminescence allowed us to trace the effect of the molybdenum inclusion on the phase purity of synthesized materials and the role of Mo in the creation of X-ray induced point defects. Oxygen-based hole trapping centers (most probably involving interstitial oxygen) as well as Mo5+-based electron trapping centers were observed and their thermal stabilities were studied. Some amount of the hole trapping centers seemed to be directly connected with the creation of Mo5+. Zinc vacancies and the Mo5+ centers up to some extent were assumed to act as recombination centers for the holes released from the hole trapping centers. The X-ray irradiation also affects the luminescence properties of the ZnO:Mo samples – the intensity of the luminescence bands in general becomes weaker. [ABSTRACT FROM AUTHOR]