The isothermal vapor-liquid equilibrium (VLE) of binary systems of thiophene + butane, + trans-but-2-ene, + 2-methylpropane, and + 2-methylpropene was measured at (308 and 336) K with a static total pressure apparatus. The measured data (temperature, pressure, and amounts of moles) were reduced to phase equilibrium data with Barker's method. All binary systems exhibited a positive deviation from Raoult's law.