The Cu–S compounds have been reported as promising thermoelectric materials with abundant element composition, low price, and low toxicity. In this work, Sn
S samples with different Sn contents (x = 0.005, 0.01, 0.03, and 0.05) were fabricated by mechanical alloying combined with spark plasma sintering. The phase structure and microstructure of all the bulk samples were checked by X-ray diffraction (XRD) and field emission scanning electron microscopy respectively. The thermoelectric transport properties, such as electrical conductivity, Seebeck coefficient, carrier concentration, carrier mobility, and thermal conductivity, were measured. The effect of second phase introduced by Sn addition on the thermoelectric properties of Cu–S system was investigated. The thermoelectric properties of samples were improved by the precipitations of two different second phases (Cu2SnS3 and Cu4SnS4). The second phase species depend on the Sn contents. Finally, the Sn0.01Cu1.79S bulk sample obtained the highest ZT value of 0.81 at 773 K, which is 1.6-fold higher than that of the pristine Cu1.8S sample due to the significantly reduced thermal conductivity by second phase and nanopores scattering.