In this study we investigated the optical properties of Cu2ZnSnSe4 monograin powders that were synthesized from binary compounds in the liquid phase of flux material (KI) in evacuated quartz ampoules. The monograin powder had p-type conductivity. Radiative recombination processes in Cu2ZnSnSe4 monograins were studied using photoluminescence spectroscopy. The detected low-temperature (T=10 K) photoluminescence band at 0.946 eV results from band-to-impurity recombination in Cu2ZnSnSe4. The ionization energy of the corresponding acceptor defect was found to be 69 +/- 4 meV. Additional photoluminescence bands detected at 0.765 eV, 0.810 eV and 0.860 eV are proposed to result from Cu2SnSe3 phase whose presence in the as-grown monograins was detected by Raman spectroscopy and SEM analysis. Considering photoluminescence results, it is proposed that the optical bandgap energy Of Cu2ZnSnSe4 is around 1.02 eV at 10 K. (C) 2008 Elsevier B.V. All rights reserved.