Gas-liquid chromatography has been used to estimate thermodynamic parameters of a variety of aromatic and aliphatic solvents at infinite dilution in poly(ethy1 methacrylate). Heats of solution, Flory-Huggins interaction parameters, and specific interaction parameters were calculated from specific retention volumes. Comparative interpretation of these thermodynamic quantities has led to the establishment of a solvent selectivity scale for poly(ethy1 methacrylate). Limitations of the threedimensional solubility parameter theory on the systems tested here are demonstrated. A significantly improved concept is developed and tested.