The isothermal vapor-liquid equilibrium (VLE) of binary systems of methoxymethane (dimethylether, DME) + thiophene, DME + 2-methylpropane-2-thiol, and DME + diethylsulfide was measured with a static total pressure apparatus. Barker's method was used to obtain phase equilibrium data from the total pressure measurements. Additionally 5 VLE data points of the binary system of 1-hexene + 1-propanethiol were measured with a glass recirculation still. The system reacted partly during the VLE measurements to form a sulfide at thiol mole fractions higher than x(1-propanethiol) = 0.1. The formation of the sulfide was verified by gas chromatographic analysis. The measured nonreacted points at low thiol concentration showed that the system 1-hexene + 1-propanethiol exhibited azeotropic behavior.