On the basis of a unique nucleophilic addition reaction, a novel water-soluble broadly emitting (500–700 nm) fluorescent Probe 1 was developed for the rapid detection of SO2 derivatives in aqueous media. The positively-charged benzopyrylium moiety in Probe 1 provides both excellent water solubility, making this probe applicable in 100% aqueous environments, and the ability to function as a fluorescence quencher of the coumarin moiety. Probe 1 generates a nearly instantaneous strong fluorescence signal in response to SO2 derivatives having an 8.3 nM detection limit for bisufite. The resulting Probe 1–sulfite adduct emits in the green/red spectral region (λmax = 585 nm) with a large Stokes shift (139 nm). The probe exhibits excellent selectivity toward SO2 derivatives over other potential interfering agents including reactive sulfur-containing species. Importantly, we demonstrate that Probe 1 can be used for the real-time sensing and bioimaging of SO2 derivatives in living cells.