Two novel coumarin-based bisulfite anion probes, 4-Methyl-8-formyl-7-hydroxylcoumarin and 4-methyl-8-formyl-7-hydroxyl-6-chlorocoumarin, were synthesized by using resorcinol and 4-chloro resorcinol as the raw material respectively. The structures of the probes were characterized by IR, 1H NMR and MS. The mechanism of determination, selectivity to bisulfite anion, analytic method and the application in the actual samples of the probes were investigated. A fluorescence analytic method for detection of bisulfite anions in water was established.