ZnSe:Sb bulk crystals were grown by a physical vapor transport technique and subsequently annealed under Se-2 partial pressure. Conduction type and net doping concentrations have been determined by capacitance voltage measurements. All the as-grown crystals are semi-insulating. After annealing, they become p-type conducting with maximum net acceptor concentrations of (7 +/- 3) x 10(16) cm(-3). The low-temperature photoluminescence of the as-grown (semi-insulating) crystals is dominated by a deep neutral acceptor bound exciton emission line and its phonon replica. After annealing, the p-type conducting samples show an intense donor-acceptor pair recombination and a shallow neutral acceptor bound exciton line appears with a binding energy of about 9.5 meV. (C) 2002 Elsevier Science B.V. All rights reserved.