Abstract The photoluminescence spectra of CuI single crystals have been studied at T = 4.2 K and at various excitation levels. The emission band of donor-acceptor pairs (DAP) with a maximum at about 4200 Å has been shown to possess a complex structure. Theoretical analyses and exciton spectroscopy data make it possible to calculate the ionization energies for the donors and acceptors participating in the formation of DAP, which are equal to E D = = 0.045−0.065 eV and E A = 0.155−0.170 eV, respectively. The fine structure of emission due to the annihilation of excitons bound on acceptor pairs (band maximum 4075 Å) has been detected and calculated. The energy of the longitudinal optical phonon participating in the exciton-phonon interaction (LO − 18.7 meV) has been determined.