There are a great amount of substances found in the must distillations and at very low concentrations (called congeners). Other than that, ethanol and water are the major compounds. These facts make it difficult to simulate and optimize this industrial process. To extend the scarce knowledge of mixing thermodynamics related to these compounds, this paper contains the results of a new experimental study of liquid-liquid equilibrium (LLE) at temperatures of (298.15, 308.15, and 318.15) K for the ternary mixtures ethanol + water + (ethyl acetate or 1-pentanol) under atmospheric conditions. Ethyl acetate and 1-pentanol are important natural and legal congeners in common alcoholic distillation. A comparative analysis was performed, by application of different group contribution methods to predict experimental equilibria behavior of these mixtures. The experimental tie line data were correlated to test consistency with the Othmer-Tobias equation. Disposable literature was revised and commented upon.