The origins for the abrupt adhesion loss at a critical relative humidity (RH) for polymeric adhesives bonded to inorganic surfaces were explored using a poly(methyl methacrylate) (PMMA) film on silicon oxide as a model system. The interfacial and bulk water concentrations within the polymer film were quantified as a function of D(2)O partial pressure using neutron reflectivity. The adhesive fracture energies of these PMMA/SiO(2) interfaces at the same conditions were determined using a shaft-loaded blister test. Discontinuities in the adhesive fracture energy, bulk moisture solubility, and the width of the interfacial moisture excess near the interface were observed at the critical RH. A mechanism based on the coupling of bulk swelling-induced stresses with the decreased cohesive strength due to moisture accumulation at the interface is proposed and is consistent with all experimental observations.