The optical properties of Cu2SnS3 (CTS) bulk crystals grown by chemical vapor transport were studied by photoluminescence (PL) spectroscopy. The PL spectra from the CTS bulk crystals were analyzed as a function of excitation power and temperature. The main phase of the as-grown samples was determined to be monoclinic CTS by Raman spectroscopy. The observed PL spectra from the CTS bulk crystals were composed of peaks corresponding to free-exciton, two bound-excitons, and donor-acceptor pair recombination luminescence. The peak energies for the free-exciton and two bound-exciton emissions were 0.9317, 0.9291, and 0.9260 eV, respectively, at temperature of 4.2 K. The bound-exciton luminescence was not observed above 30 K. The thermal activation energies for the free-exciton and two bound-exciton emissions were 6.5, 4.8, and 5.2 meV, respectively. The fundamental band gap in the CTS bulk crystals was expected to be ca. 0.94 eV.