A novel near-infrared-emitting aza-BODIPY-based fluorescent probe with two tellurium atoms at two upper benzyl rings has been prepared and explored for its fluorescent sensing properties towards hypochlorous acid/hypochorite (HClO/ClO−), which showed high selectivity and absolutely fluorescent “turn-on” phenomenon at 738 nm. The fluorescence of this probe was sufficiently quenched due to photoindued electron transfer by two tellurium atoms. Upon exposure to HClO/ClO−, a strong near-infrared emission at 738 nm appeared with fluorescence quantum yields changing from 0 to 0.11. This remarkable fluorescence change was ascribed to the oxidation of both electron-rich tellurium atoms. The detection limit of this probe towards HClO/ClO− was calculated to 0.09 μM in acetonitrile aqueous solution by the linear fluorescence change at 738 nm in the HClO/ClO−-concentration range of 0–30 μM. Interestingly, this probe was found to be applicable in a broad pH range (2–10). Meanwhile, the oxidized probe could be further responsive to biothiols with substantial fluorescence disappearance. The bioimaging experiments in RAW264.7 cells showed the appearance of intracellular near-infrared fluorescence after addition of HClO/ClO− and PMA, and the fluorescence could also be reversed to be silenced by further introduction of GSH, confirming its potential application for exogenous and endogenous detection of HClO/ClO− in living cells.