The isobaric vapor-liquid equilibrium data for distillation have been measured for three binary systems of (1,2-butanediol(BD)+1,4-BD), (1,2-BD+2,3-BD), and (1,4-BD+2,3-BD) and for the ternary system of (1,2+BD+1,4-BD+2,3-BD) at 101.3 kPa. The thermodynamic properties of the vapor phase have been calculated with the Hayden-O'Connell equation in consideration of nonideality. The liquid activity coefficients have been satisfactorily correlated with the Wilson, NRTL and UNIQUAC models. The corresponding binary interaction parameters of the three models were calculated. Based on all the preceding results, a two-column distillation process was designed to obtain the required products with purity of 98% for industrial use.