Photoluminescence (PL) spectra of TlInSeS layered single crystals were investigated in the wavelength region 46.0-800 nm and in, the temperature range 10-65 K. We observed one wide PL band-centred at 584 nm (2.122 eV) at T = 10 K and an excitation intensity of 7.5 W cm(-2). We have also studied the variation of the PL intensity versus excitation laser intensity in the range from 0.023 to 7.5 W cm(-2). The red shift of this band with increasing temperature and blue shift with increasing laser excitation intensity was observed. The PL was found to be due to radiative transitions from the moderately deep donor level located at 0.243 eV below the bottom of the conduction band to the shallow acceptor level at 0.023 eV located above the top of the valence band. The proposed energy-level diagram permits us to interpret the recombination processes in TlInSeS layered single crystals.