Photoluminescence measurements were carried out in order to investigate the dependence of the optical properties ofp‐Cd0.96Zn0.04Te single crystals on hydrogen passivation conditions. After thep‐Cd0.96Zn0.04Te was annealed at 500 °C in a Cd atmosphere for 5 h, the luminescence due to the recombination of the electrons in the conduction band with acceptors (eA°) and to the donor–acceptor pair (DAP) transitions disappeared. After thep‐Cd0.96Zn0.04Te was hydrogenated, the intensity of the exciton luminescence increased so that the (eA°) and DAP peaks related to the Cd vacancies disappeared, and the defect band in the low energy range between 1.4 and 1.5 eV also vanished. These results indicate that hydrogen atoms passivated not only shallow donors but also deep acceptor impurities and that the hydrogen atoms were separated from the hydrogenated samples at 400 °C due to their thermal energy.