The reconstruction of the bound excitonic spectra of MOVPE-grown ZnSe:N samples caused by thermal annealing was observed. The results of the low temperature photoluminescence, reflection and SIMS measurements show that this reconstruction is caused neither by the strain effect nor by the removal of hydrogen from the samples. The calculation of the defect structure and energy by the SCF MO LCAO method was carried out, and a new stable configuration of the N se center has been found. A model of reconstruction of the nitrogen centers is proposed, assuming that the transition of N Se centers from a less stable state with distorted T d configuration into the energetically more favorable distorted C 3v configuration occurs due to thermal annealing, resulting in the corresponding changes in the luminescence spectra.