When adhesives and/or composites are bonded to the tooth, water in the environment can interfere with proper interface formation. Formation of water blisters and phase separation at the adhesive/dentin interface have appeared as new types of bond defects. To better understand this problem, we determined the near-equilibrium partition of the hydrophobic/hydrophilic components when exposed to over-wet environments. Model methacrylate-based adhesives were mixed with different amounts of water to yield well-separated aqueous and resin phases. It was found that less than 0.1% BisGMA but nearly one-third of the HEMA diffused into the aqueous phase, leaving the remaining resin phase relatively hydrophobic. A partial phase diagram was created for the ternary BisGMA/HEMA/water system. All the experimental phase partitioning data were plotted, and the points lay on a binodal curve that separated the single-phase region from the two-phase region. We obtained the 3 tie lines by connecting the 2 points of each conjugate pair of the phase partitioning data from the 3 sets of tripartite mixtures. Information about solubility, water miscibility, distribution ratio, and phase partitioning behavior could be obtained quantitatively. This type of phase diagram will provide a more thorough understanding of current adhesive performance and elucidate directions for further improvement.