The adhesion of photocured resins to ceramic substrates has been investigated using a variety of surface analytical techniques. Work has been aimed at establishing the physical and chemical interactions between resin and substrate in the interphase region and the effect of environmental exposure on these. Analysis was aided by use of specially-designed, in-situ fracture facilities attached by an X-ray photoelectron spectrometer. Specific attention was focused on identification of localised regions of varying chemical composition in adhesive and adherend by imaging spectroscopies (imaging XPS and ToF SIMS imaging) and the study of the significance of such heterogeneities on adhesion and subsequent failure mechanisms.