In this work, a novel curing-induced fluorescence (FL) enhancement phenomenon in the nanostructuring process of epoxy thermosets was investigated. Toward this end, a diblock copolymer composed of poly(ethylene oxide) and poly(((4-vinylphenyl)ethene-1,1,2-triyl)tribenzene) (PTPEE) blocks was introduced into epoxy thermosets. Before curing reaction, the mixtures of epoxy precursors with the diblock copolymer only emitted feeble FL under ultra-visible (UV) irradiation. However, photoluminescence was significantly enhanced after the curing reaction was carried out. It was found that the novel FL enhancement phenomenon resulted from the aggregation-induced emission behavior of PTPEE blocks, which was triggered by curing reaction. In the nanostructured thermosets, the fluorophore blocks (viz. PTPEE) of this diblock copolymer were segregated into aggregates, that is, a reaction-induced microphase separation occurred. Owing to the generation of PTPEE microdomains, the epoxy nanocomposites significantly displayed the enhanced dielectric constants due to the promoted contribution from electron polarizations via pi-pi conjugation in the materials.