The results of the study of optical absorption and EPR signals of single crystals of zinc oxide doped with manganese are presented. A broad impurity absorption band with the threshold energy about 2.1 eV, which was treated as a result of charge transfer transitions, has been observed for a long time in ZnO : Mn absorption spectra. In absorption spectra of a polarized light at 4.2 and 77.3 K, we first detected several lines of different intensity in a 1.877–1.936 eV range of energies of the light quanta. The observed lines are attributed to a donor exciton [( d ^5 + h ) e ] that emerges as a result of the Coulomb binding a free s electron and a hole, which is localized on p – d hybridized states. The EPR spectra of Mn^2+ ion signals, when corresponding to the impurity absorption band exposed to light, are found to be not photosensitive. The obtained results indicate that the ZnO : Mn impurity absorption is due to transitions from antibonding p – d hybridized DBH states to the conduction band.