Sulfur dioxide (SO2) derivatives are intertwined with many physiological and pathological processes in living systems, and excess intake of them are associated with various diseases. Herein, we have rationally constructed a novel colorimetric and far-red fluorescent probe for HSO3− based on a rhodamine analogue skeleton bearing a 3-quinolinium carboxaldehyde moiety. The novel probe exhibited a significant far-red fluorescence “Turn-on” response to HSO3−, along with obvious color change from reddish to purple via the specific 1,4-nucleophilic addition reaction of HSO3− with the quinolinium moiety in 3-(4-(2-carboxyphenyl)-7-(diethylamino)chromenylium-2-yl)-1-methylquinolin-1-ium hypochlorite trifluoromethanesulfonate (AQCB). The AQCB had excellent water-solubility, and presented rapid response (<15 s),highsensibility(LOD = 49 nM) and selectivity toward HSO3−. In addition, the probe was able to detect the content of HSO3− in food samples with satisfactory results. Furthermore, the probe possessed good cell membrane and could be successfully applied for imaging HSO3− in the mitochondria of living cells.