A detailed interpretation of exciton lines caused by the presence of a lithium impurity in ZnO crystals (T = 4.2 K) was carried out. The 368.5-nm line is caused by radiative recombination of excitons bound on neutral donor states $$ {Li}_i^{\times } $$ . The 371.2-nm line is caused by the same process but occurring simultaneously with the transition of the donor to the excited state. The 368.2-nm line occurs when excitons bound on ionized $$ {Li}_i^{+} $$ states emit. The 369.7-nm line is the emission of excitons bound on acceptor complexes of the form ( $$ {Zn}_i^{+}{Li}_{Zn}^{\mid } $$ ), ( $$ {In}_{Zn}^{+}{Li}_{Zn}^{\mid } $$ ), ( $$ {Li}_i^{+}{Li}_{Zn}^{\mid } $$ ), etc. The measurements also made it possible to calculate the ionization energy of shallow donors $$ {Li}_i^{\times } $$ as Ed = 0.033 eV. Thus, a method for exciton spectroscopy of lithium states affecting the optical and electrophysical characteristics of zinc oxide has been developed.