Formation of a single‐component charge‐transfer complex (SCCTC) is unveiled in solid state of an intermolecular charge‐transfer molecule 2‐(4‐(1‐phenyl‐1H‐phenanthro9,10‐dimidazol‐2‐yl)phenyl)anthracene‐9,10‐dione (PIPAQ). Intermolecular donor–acceptor interactions between two PIPAQ molecules is the primary driving force for self‐association and contributes to intermolecular charge transfer. The SCCTC character is fully verified by crystallographic, photophysical, electron spin resonance, and vibrational characterizations. The PIPAQ‐based SCCTC is first applied in light‐emitting devices as an emissive layer to realize efficient deep‐red/near‐infrared electroluminescence. This work provides new insights into SCCTC and represents an important step toward their applications in optoelectronic devices. Dimeric single‐component charge‐transfer complexes (SCCTCs) by self‐complexation of a donor–π–acceptor molecule (PIPAQ) are revealed and fully investigated, wherein the strong intermolecular charge transfer leads to unprecedented deep‐red/near‐infrared emission. The SCCTCs can be formed in thin films and applied in electroluminescence devices to realize high efficiencies via a thermally activated delayed fluorescence channel.