The ability for polymers and additives to physically mix in many industrial applications is dictated by a combination of kinetic and thermodynamic factors. The presence of moisture may complicate the mixing performance as water can interact at various degrees with each of the components; this depends on the hydrophilicity of the materials. In this study, the physical mixing behavior of a ternary system consisting of a hygroscopic polymer (copovidone), a plasticizer, and water was examined. Three different liquid plasticizers with a range of hydrophilic-lipophilic properties and viscosities were evaluated for their physical mixing performance and the impact of their water content. Inverse gas chromatography was introduced as a new method for measuring the surface characteristics of the physical mixtures to quantify the mixing performance. Through the application of the Flory-Huggins model to understand the thermodynamic behavior of the system, it was shown that mixing was less effective in a system of high water content for a hydrophobic plasticizer. However, the underlying thermodynamic unfavorability of such a system could be overcome by kinetic influence to provide a good mixing performance. Specifically, as the viscosity of the plasticizer decreased, the influence of the thermodynamic characteristics was found to become less apparent.