In this work, vapor−liquid equilibrium (VLE) measurements of propyl mercaptan (PM) in pure water were performed at three different temperatures, (303, 323, and 365) K, with a pressure variation from (1 to 8) MPa. The total system pressure was maintained by CH4. The inlet mole fraction of propyl mercaptan in all experiments was the same, around 4.5·10−4 in the liquid phase. The objective was to provide experimental VLE data points of the propyl mercaptan + methane + water system for modeling since there is a lack of available data. These data will allow the industrial modeling of sulfur emission. The thermodynamic model used for the description of VLE is the extended UNIQUAC model. The model parameters are valid in the temperature range similar to the measured data and a pressure range up to 8 MPa.