The volatilization kinetics of antimony trisulfide in steam atmosphere was studied with thermogravimetry at temperatures from 923 to 1123 K. A theoretical model was developed to calculate the overall rate constant and the mass transfer coefficient in gas phases. The experimental results show that the volatilization rate is enhanced with increasing temperature and steam flow rate. The volatilization rate is mainly controlled by the mass transport in gas phases. The apparent activation energy for the process is found to be 59.93 kJ/mol. It is demonstrated that Sb2S3is dominantly oxidized into Sb2O3 and H2S by water vapor in the volatilization process. Some antimony metal is formed. The reaction mechanism is discussed in accordance with experimental data.