Amorphous, non-doped, and copper- and selenium-doped Sb2S3 nanoparticles were synthesized by a hot-injection method. Zinc-doped Sb2S3 nanoparticles were prepared for the first time using the same approach. Electron microscopy revealed that spherical nanoparticles of 1–4 nanometers aggregated into larger spherical clusters. Introducing dopants into the Sb2S3 structure neither influenced the samples’ spherical morphology nor their sizes. The presence of the dopants (Cu, Se, or Zn) was confirmed by energy dispersive X-ray (EDX) and, in the case of Zn, also by inductively coupled plasma-mass spectrometry (ICP-MS). The X-ray powder diffraction (XRPD) patterns of the non-doped and doped samples imply an amorphous structure. Crystalline Zn-doped Sb2S3 revealed defined peaks from only the Sb2S3 phase, indicating successful doping. Diffuse reflectance spectroscopy (DRS) revealed high optical bandgap energies (2.03–2.12 eV) compared to the values (1.6–1.7 eV) for large non-doped and doped particles obtained at 240 °C, which might be attributed to a quantum size effect. X-ray photoelectron spectroscopy (XPS) revealed a phase without any impurities for the undoped and characteristic peaks for copper, selenium, and zinc Auger for the doped samples. XPS valence band confirm for the Zn-doped particles a shift towards lower binding energy compared to the non-doped samples, indicating successful doping. Photoluminescence (PL) measurements show that embedding Zn into the Sb2S3 host lattice suppresses the wide luminescence band related to intrinsic vacancy defects. Narrow peaks at 1.7–2.4 eV were found to be associated with singlet excitons. The energy dependence of the light emission on the synthesized nanoparticles’ size suggests quantum confinement. © 2023, The Author(s), under exclusive licence to Springer Nature B.V.