The objective of this study is to carry out nanoscale characterization of the epoxy resin interface on silica by determining the glass-transition temperature (Tg) and molecular conformation at the interface by means of a novel non-destructive method. The Tg was determined by fluorescence lifetime measurements using evanescent wave excitation. It was revealed that the Tg of epoxy resin at a distance of 30 nm from the interface was 10 K higher than that at a distance of 80 nm. The chemical composition and molecular conformation were analysed by X-ray photoelectron spectroscopy and sum-frequency generation (SFG) spectroscopy, respectively. The SFG data revealed that unreacted epoxy group remained at the interface. The Tg of epoxy resin increased in the regions near the interface, and the epoxy group remained unreacted at a distance of ca. 10 nm or less from the interface.