Аннотация:The new method of nonstoichiometry investigation in the metal-organic (MO) crystalline materials has been developed. Using a quasi-closed ampoule system the method allowed monitoring the changes in fluorescent characteristics of metal–organic samples with temperature, annealing time and partial pressure of ligand-forming substance (pL) in situ. When combined with X-ray analysis the method made it possible to find the conditions for the synthesis of single-phase metal-organic crystalline samples with a certain disordering in the crystal lattice determined by atomic defects similar to the nonstoichiometry phenomenon in classic semiconductors. The influence of pL and temperature on structural and luminescent properties of MO crystalline samples (99.9985 wt%) has been also studied for the samples quenched after annealing’s. It was found that direct changes of pL at the fixed annealing temperature caused the systematic changes of photoluminescent spectra maximum, decay kinetics and structural characteristics.