Intracellular lipid droplets (LDs) are important organelles regulating intracellular redox processes. Endogenous bisulfite/sulfite (HSO3−/SO32−) is one of the metabolites of thiol metabolism. The variation in HSO3−/SO32− content around LDs is closely related to cellular homeostasis. However, there is currently no effective method to visualize and quantify the dynamic changes in HSO3−/SO32− content around LDs. In this work, a fluorescent probe MC-BEN utilizing a triphenylamine basic framework was developed to selectively recognize HSO3−/SO32− via a nucleophilic addition reaction. The probe exhibits excellent anti-interference capability, short response time, outstanding photostability, and a low fluorescence detection limit (6.1 μM) for HSO3−/SO32− recognition. More interesting, there is a trend of accelerated contact between LDs and lysosomes after MC-BEN targeting LDs and reacting with endogenous/exogenous HSO3−/SO32−, which may provide new ideas for the study of intracellular lysosomal lipophagy.