Antimony sulfide (Sb2S3) has been applied in photoelectric devices for a long time. However, there was lack of information about Sb2S3 quantum dots (QDs) because of the synthesis difficulties. To fill this vacancy, water-soluble Sb2S3 QDs were prepared by hot injection using hexadecyltrimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) mixture as anionic-cationic surfactant, alkanol amide (DEA) as stabilizer, and ethylenediaminetetraacetic acid (EDTA) as dispersant. Photoelectric properties including absorbing and emission were characterized by UV-Vis-IR spectrophotometer and photoluminescence (PL) spectroscopic technique. An intensive PL emission at 880 nm was found, indicating Sb2S3 QDs have good prospects in near-infrared LED and near-infrared laser application. Sb2S3 QD thin films were prepared by self-assembly growth and then annealed in argon or selenium vapor. Their band gaps (Egs) were calculated according to transmittance spectra. The Eg of Sb2S3 QD thin film has been found to be tunable from 1.82 to 1.09 eV via annealing or selenylation, demonstrating the good prospects in photovoltaic application.