Information on water transport along the polymer/substrate interface is valuable for understanding the mechanisms and the controlling factors affecting the water-induced adhesion loss of polymer-coated metals, adhesive-bonded joints, and polymer/fiber composites subjected to aqueous environments. This paper presents data to demonstrate the capability of a technique, which combines a vertical cell with Fourier transform infrared spectroscopy in the multiple internal reflection mode, for studying water transport along the polymer/substrate interface and interfacial hydrolytic stability of polymeric composites and systems exposed to water and high relative humidities. The technique can distinguish water transport through the film from that along the interface; the latter transport is predominant for polymer/untreated substrate systems. Spectroscopic analyses of fractured surfaces of poor and well-bonded polymer/substrate systems after water exposure indicate that the technique is capable of discerning a hydrolytically-stable interface from a water-susceptible interface.