Hypochlorite, as an important reactive oxygen species (ROS), plays a vital role in many physiological and pathological processes, but an excess concentration of hypochlorite (ClO-) may become toxic to humans and cause disease. Hence, the selective and rapid detection of hypochlorite (ClO-) is necessary for human safety. Here, we report a novel near-infrared (NIR) fluorescence "turn-on" and highly selective benzophenoxazinium chloride-based fluorescent probe, BPH (benzophenoxazinium dihydroxy benzaldehyde), for hypochlorite detection. Due to hypochlorite-induced vicinal diol oxidation to the corresponding ortho benzoquinone derivative, the photoinduced electron transfer (PET) process, which was operating from vicinal diol to the benzophenoxazinium chloride receptor moiety, was suddenly inhibited, as a result of which strong NIR fluorescence "turn-on" emission was observed. The detection limit of BPH was found to be 2.39 × 10-10 M, or 0.23 nM. BPH was successfully applied for exogenous and endogenous hypochlorite detection in live MDA-MB 231 cells.