Abstract We intend to search a new method to prepare high-quality and large-size p-ZnSe single crystal. In this study, ZnSe:Li3N single crystal is grown by a vertical Bridgman method using a closed double-crucible. The photoluminescence (PL) spectrum of the as-grown ZnSe:Li3N crystal at 8 K shows very strong donor–acceptor pair (DAP) and very weak exciton emissions. In order to activate doped Li3N, ZnSe:Li3N single crystal is annealed at high temperature in Zn-saturated atmosphere. By selecting suitable annealing conditions, a very strong I1 emission line related to shallow acceptor is observed. The capacitance–voltage (C–V) characteristics indicate that the annealed ZnSe:Li3N single crystal is a p-type conduction. Furthermore, the acceptor concentration and ionization energy are estimated by examining the temperature dependences of the free-to-acceptor (FA) emission, the behaviors of Li and N are investigated, and the new emission at 2.34 eV is discussed.