Chemical bath–deposited cadmium sulfide (CBD-CdS) is the most widely used buffer layer material for antimony selenosulfide (Sb2(S,Se)3) photovoltaic devices, but its medium band gap, large band gap offset with transparent conducting oxides, and surface defects must be addressed to improve its applicability. Hexagonal CdS films (60 nm thick) prepared using the thermal evaporation method were used as the buffer layers of Sb2(S,Se)3 photovoltaic devices. Compared with CBD-CdS (60 nm thick), thermal evaporation–deposited CdS (TED-CdS) films have a larger band gap and fewer surface defects. The Sb2(S,Se)3 film deposited on TED-CdS is more compact, and its 1D ribbons are stacked more vertically to the substrate. The band gap offset between CdS and fluorine-doped tin oxide glass decreases from 0.76 eV (CBD-CdS) to 0.60 eV (TED-CdS). Therefore, suppressed electron trap density and charge recombination, as well as improved light harvesting, are achieved. By replacing CBD-CdS with TED-CdS, the best device efficiency increases from 6.14 % to 7.16 %, with the open circuit voltage, short-circuit current density, and fill factor increasing from 0.660 V, 15.96 mA/cm2, and 58.37 % to 0.664 V, 17.39 mA/cm2, and 62.85 %, respectively. The device stability and reproducibility are also improved.