Bulk ZnO grown by the hydrothermal technique was investigated using electron paramagnetic resonance (EPR), photoluminescence (PL), and infrared absorption (FTIR) techniques. Isolated subsitutional lithium is the dominant acceptor and could be detected using EPR or PL. A large concentration of neutral Li+-OH− centers were observed using FTIR data. EPR spectra assigned to Mn, Co, Ni, Fe, and Group III (Al, Ga) donors were also observed. Photoinduced changes in the charge states of the different deep and shallow centers were produced using 325 nm light, and the stability of these changes were monitored with EPR during pulsed thermal anneals. The charge-state changes for some defects were persistent and remained up to 300 K. These impurities, when present in device structures, may act as stable charge trapping sites.