The principal results of the investigation of thermally stimulated electron–hole and ionic processes in hydrothermal and gas-phase ZnO single crystals preexcited at low temperatures, based on simultaneous study of photo-EPR and thermoluminescence (TL), are presented. The nature of the traps determining the TL peaks at 17, 24, 40, 53, 90–110, 140–150, and 160–200 K is discussed. In particular, it has been established that the lithium paramagnetic centers (LiZn+–OI) play the role of hole traps in ZnO giving green and red TL in the temperature range 160–200 K and, in the case of association with small-sized donors, also TL in the temperature range 90–110 K. The other traps are electronic in character, and in the presence of acceptor lithium in the crystals, they form yellow-orange TL. Optical quenching of TL has been evaluated, and it has been found that there is a difference ΔE ≈ 0.75 eV between the thermal and optical energies of ionization of lithium acceptors. Irreversible ionic processes associated with the “healing” of cationic vacancies at T ≈ 360–420 K have been revealed.