Chemiluminescence　(CL)　is　a　self-illuminating　phenomenon　fueled　by　chemical　energy　instead　of　extra　excited　light,　which　features　superiority　in　sensitivity,　signal-to-background　ratios,　and　imaging　depth.　Strategies　to　synthesize　a　CL　emission　unimolecular　skeleton　in　the　second　near-infrared　window　(NIR-II)　and　a　unimolecular　probe　with　direct　duplex　NIR-II　[CL/fluorescence　(FL)]　emission　are　lacking.　Here,　we　employ　modular　synthesis　routes　to　construct　a　series　of　directly　activated　NIR-II　CL　emission　unimolecular　probes　with　a　maximum　emission　wavelength　of　up　to　1060　nm,　and　use　them　for　real-time　and　continuous　detection　of　the　superoxide　anion　generated　in　acetaminophen　induced　liver　injury　in　a　female　mice　model　under　both　NIR-II　CL　and　NIR-II　FL　imaging　channels.　Thus,　this　study　establishes　a　directly　activatable　NIR-II　CL　emission　unimolecular　skeleton,　validating　the　scalability　of　this　duplex　NIR-II　CL/FL　imaging　platform　in　bioactive　molecule　detection　and　disease　diagnosis.