Identification of early damage in polymer composites is of great importance. We have incorporated cyclobutane-containing crosslinked polymers into an epoxy matrix, studied the effect on thermal and mechanical properties and more importantly, demonstrated early damage detection through mechanically induced fluorescence generation. Two cinnamate derivatives, 1,1,1-tris(cinnamoyloxymethyl) ethane (TCE) and poly(vinyl cinnamate) (PVCi), were photoirradiated to produce cyclobutane-containing polymer, respectively. The effects on the thermal properties and mechanical properties with the addition of cyclobutane-containing polymer into epoxy matrix were investigated. The emergence of cracks was detected by fluorescence at a strain level right beyond the yield point of the polymer blends and the fluorescence intensified with accumulation of strain. Overall, the results show that the damages can be detected through fluorescence generation along the crack propagation.