Near-infrared photoluminescence (PL) and thermally stimulated current (TSC) spectra of Cu3Ga5Se9 layered crystals grown by Bridgman method have been studied in the photon energy region of 1.35-1.46 eV and the temperature range of 15-115 K (PL) and 10-170 K (TSC). An infrared PL band centered at 1.42 eV was revealed at T = 15 K. Radiative transitions from shallow donor level placed at 20 meV to moderately deep acceptor level at 310 meV were suggested to be the reason of the observed PL band. TSC curve of Cu3Ga5Se9 crystal exhibited one broad peak at nearly 88 K. The thermal activation energy of traps was found to be 22 meV. An energy level diagram demonstrating the transitions in the crystal band gap was plotted taking account of results of PL and TSC experiments conducted below room temperature. (C) 2016 Elsevier B.V. All rights reserved.