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Sulfite and sulfide share several similarities in terms of chemical properties, such as nucleophilic and reducing reactivities. Therefore, they may disturb the detection of each other. In order to discriminate between these two kinds of sulfur-containing species, a new probe TSSP-N3 was developed, in which para-azidobenzenyl ketone was covalently incorporated to a coumarin fluorophore linked by a C=C double bond. Sulfite and sulfide can respectively react with the C=C double bond and the azido group to give different products, consequently, they can be differentially identified by UV-vis and fluorescence spectroscopy as well as by the naked eye. Selectivity and competition results reveal that TSSP-N3 is a good candidate for the detection of sulfide and sulfite. The bioimaging experiment demonstrates the potential of the TSSP-N3 probe for the differential imaging of sulfide and sulfite in living cells. [ABSTRACT FROM AUTHOR]