we extend this analysis to ternary mixtures of the same components. New isobaric vapor−liquid equilibrium data have been measured for four ternary mixtures including 1-propanol/2-butanone/ethyl acetate, 1-propanol/2butanone/methyl propionate, 1-propanol/2-butanone/propyl formate, and 1-propanol/2-butanone/2-propanol at P = 1.013 bar. In this way, the role of different functional groups in the third component of dipolar, solvating mixtures could be assessed systematically and compared to the previously measured binary mixtures. Such a systematic data measurement approach also aids thermodynamic model development and assessment. Such a preliminary assessment was conducted using the sPC-SAFT equation of state, combined with the GV, and JC polar terms, applied to predict the phase equilibria of the studied ternary mixtures. Molecular solvation was accounted for by assigning a single-electron donor site to the ketone and ester species. Phase equilibria of the studied ternary mixtures were predicted without any adjustable parameters, i.e., the binary interaction parameters were set to zero (k ij ). The results for the multicomponent mixture were consistent with the previous binaries, where accounting for solvation is the most important consideration. Moreover, model shortcomings in the binary systems appear to propagate, rather than average out, in the complex solvation of multicomponent mixture, emphasizing the need for accurate parameterization and systematically measured mixture data.