The effects of absorbed water on the interfacial fracture resistance between two layers of unsaturated polyester (UP) and glass of the bilayer specimen were evaluated by measuring a load for producing the fracture by inserting a razor blade into the interface. The specimens were subjected to the cyclic absorption-desorption and the continuous absorption processes of water. The load to initiate the interfacial fracture was markedly lowered by the early absorption process for short period, and then gradually reduced with increasing cycle or period of water absorption, although it slightly recovered after the first great reduction when the specimens were subjected to the soaking process at lower temperatures. The micro-FTIR (ATR) analyses of the detached surface of the UP resin from the glass plate revealed that the water is accumulated in the resin at the interface in the cluster, showing the concentration to increase with increases both in the temperature of environmental water and in the water-soaking period. The IR analyses also demonstrated the hydrolysis reaction to take place on the detached resin surface of specimen exposed to water at high temperature. Thus the accumulated water at the interface may remain and promote the interfacial degradation even under the drying process by various mechanisms like the hydrolysis reaction in hot water environment.