Aims-The purpose of this study was to evaluate the effects of a polymerizable solubility enhancer, poly (ethylene glycol) dimethacrylate (PEGDMA) in BisGMA/HEMA model adhesives on adhesive phase separation, adhesive penetration and structural integrity of adhesive/dentin (a/d) interfaces.Materials and methods-the occlusal one-third of the crown was removed from 10 unerupted human third molars, each tooth was separated in half by cutting perpendicular to the acid conditioned dentin surface and treated with BisGMA/HEMA model adhesives with and without PEGDMA. Fivemicron-thick sections of adhesive/dentin interface specimens were cut and stained with Goldner's trichrome for light microscopy. Companion slabs were analyzed with micro-Raman spectroscopy and scanning electron microscopy (SEM). The macrophase separation in the model adhesives with/ without PEGDMA was also detected using cloud point measurements in the presence of water.Results-The addition of PEGDMA enhanced the water solubility/compatibility of the BisGMA/ HEMA model adhesives. Micro-Raman spectral analysis of the dentin/adhesive interface indicated that there was a gradual decrease in penetration of BisGMA component for model adhesive without PEGDMA, while homogeneous distribution of the hydrophobic BisGMA component was noted in the interface with adhesive containing PEGDMA. The addition of PEGDMA dramatically facilitated infiltration of the hydrophobic monomers into the wet demineralized dentin. The SEM and staining results showed that the addition of PEGDMA would also improve the integrity at the interface between pure adhesive and hybrid layers.Significance-The addition of PEGDMA could reduce phase separation, enhance the infiltration of BisGMA-based adhesives into the wet, demineralized dentin substrates, and promote homogeneous distribution of the hydrophobic component throughout the interface.