The acetate derivatives of coumarin exhibited a prominent turn-on type signaling behavior toward BO(3)(-) ions over other common anions. Signaling is based on the selective deprotection of acetate groups by perborate, which resulted in significant fluorogenic signaling in an acetate buffered solution (pH 5.0). Interestingly, the detection process makes the raw material of 7-hydroxycoumarin regenerate, and the probe could be applied for the detection of BO(3)(-) of thimerosal. Furthermore, the optical properties of the probe and its BO(3)(-)-induced product were theoretically studied based on density functional theory (DFT) and the time-dependent DFT (TDDFT) explored at the B3LYP/6-311+G (d, p) level.