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We have designed two mitochondria targetable probes P-Py and P-An by the π-conjugation of polyaromatic hydrocarbons (pyrene vs. anthracene) with 4-dimethylamino pyridinium. They present an amphiphilic property with excellent solubility in the common polar and non-polar solvents. Both of them demonstrated a significant fluorescence response to bisulfite in Tris-HCl buffer solutions (5 mM, pH = 7.4). By a combination of fluorescence, UV-vis, time-resolved emission, 1H NMR, and ESI-MS, their sensing mechanisms have been elaborated to be a