The Butler equation is employed to describe quantitatively the nature, properties, and compositions of surface layers in binary liquid mixtures. Bulk mole fraction, surface molar area, and surface tension of pure components are necessary inputs for this equation. In addition, the UNIFAC group contribution method is applied to account for the nonideality of the bulk liquid as well as that of the surface layer. The average relative error obtained from the comparison of experimental and calculated surface tension values for 12 binary systems is less than 1%. Therefore, the model has good accuracy in comparison with other predictive equations. In addition to finding more information about the surface structure of binary mixtures, surface mole fraction was calculated using relative Gibbs adsorption values and an extended Langmuir model (EL). The obtained results show a good consistency between two models employed, i.e., the Gibbs adsorption model and EL model, based on the UNIFAC method. (C) 2008 Elsevier Inc. All rights reserved.