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In this work, we developed a facile end-functionalization method using hydroxylated coumarin to initiate the ring-opening polymerization of cyclic esters to synthesize a series of fluorescent biodegradable aliphatic polyesters with tailorable properties. The resulting fluorescent functionalized poly(l-lactide) (PLLA-COU), poly(ε-caprolactone) (PCL-COU) poly(δ-valerolactone) (PVL-COU) and poly(trimethylene carbonate) (PTMC-COU) were investigated to evaluate the dependence of fluorescence on the chemical structure and molecular weight of