The photoluminescence (PL) spectra of TlGaSe2 layered single crystals were investigated in the 8.5-35 K temperature. 0.2-15.2 W cm-2 excitation laser intensity, and in the 600-700 nm wavelength range. The PL spectrum has a slightly asymmetric Gaussian lineshape with a peak position located at 1.937 eV (640 nm) at 8.5 K. The PL is quenched with increasing temperature. The blue shift of the PL peak and the sublinear increase of the PL intensity with increasing laser intensity is explained using the inhomogenously spaced donor-acceptor pair recombination model. Analysis of the data indicates that the PL band is due to donor-acceptor recombination. A shallow acceptor level and a moderately deep donor level are, respectively, introduced at 0.012 eV above the top of the valence band and at 0.317 eV below the bottom of the conduction band. An energy-level diagram for radiative donor-acceptor pair recombination in TlGaSe2 layered single crystals is proposed.