Polymer matrix composites (PMCs) are ubiquitous in engineering applications due to their superior mechanical properties at low weight. However, they are susceptible to damage due to their low interlaminar mechanical properties and poor heat and charge transport in the transverse direction to the laminate. Moreover, methods to inspect and ensure the reliability of composites are expensive and labor intensive. Recently, mechanophore-based smart polymer has attracted significant attention, especially for self-sensing of matrix damage in PMCs. A cyclobutane-based self-sensing approach using 1,1,1-tris (cinnamoyloxymethyl) ethane (TCE) and poly (vinyl cinnamate) (PVCi) has been studied in this paper. The self-sensing function was investigated at both the polymer level and composite laminate level. Fluorescence emissions were observed on PMC specimens subjected to low cycle fatigue load, indicating the presence of matrix cracks. Results are presented for graphite fiber reinforced composites.