Interfacial degradation behavior of E-glass cloth reinforced vinyl ester resin under acidic conditions has been investigated. Specimens with different surface treatment conditions were prepared. Mode I fracture toughness tests were performed using DCB specimen, and the effect of surface treatment condition and immersion time on the crack propagation behavior is discussed. The crack propagation behavior changes as a function of the condition of the silane coupling agent and the immersion time due to the degradation of the interphase. A technique is proposed to evaluate the interfacial property. The change of fracture toughness of interphase and resin as a function of immersion time is studied by the crack propagation behavior and the fracture toughness of interphase and resin evaluated by this technique. The fracture toughness of interphase decreases rapidly with immersion in acidic solution.