Isothermal vapor pressures of three binary systems, methyl dodecanoate (1) + n-tetradecane (2); methyl tetradecanoate (1) + n-tetradecane (2); and methyl hexadecanoate (1) + n-tetradecane (2), were measured by means of a static apparatus at temperatures between 353.15 and 453.15 K. The data of the pure components were correlated by the Antoine equation. A maximum azeotropic behavior is observed for the binary mixture, methyl dodecanoate (1) + n-tetradecane (2). The molar excess Gibbs energies G(E) were deduced from Barkers method by fitting the experimental points through Redlich-Kister equation. The NRTL and UNIQUAC models were applied to regress the experimental vapor liquid equilibrium (VLE). The investigated systems were successfully represented by the two models.