Isobaric vapor–liquid equilibrium (VLE) data is determined for the binary mixtures of N-methyl-2-pyrrolidone + aminoethanol, N-methyl-2-pyrrolidone + chloroethanol, and N-methyl-2-pyrrolidone + phenylethanol at 95.3 kPa over the entire composition range using a Swietoslawski type ebulliometer. All three systems investigated show negative deviations from Raoult's law, and none of the binary systems formed azeotropic mixtures. The experimental VLE data of the three binary mixtures are correlated using the Wilson model. The computed vapor phase mole fractions, activity coefficients, and Gibbs energy along with optimum Wilson parameters are presented. The studies indicate that all three binary systems are nonideal liquid mixtures deviating from Raoult's law exhibiting negative values of excess Gibbs energies due to strong intermolecular hydrogen bonding between unlike molecules.