Isothermal vapor- liquid equilibrium ( VLE) for thiophene + n- hexane at ( 338.15 and 323.15) K and thiophene + 1- hexene at ( 333.15 and 323.15) K were measured with a circulation still. Maximum pressure azeotropes were found in the thiophene + n- hexane system. Azeotropic behavior was not found for the thiophene + 1- hexene system. The experimental results were correlated with Wilson model and also compared with original UNIFAC, UNIFAC- Dortmund, and COSMO- RS predictive models. Analyses of liquid and vapor- phase composition were determined with gas chromatograph and refractometer. All VLE measurements passed the three thermodynamic consistency tests used.