Herein, we report a deep‐red TADF emitter pCNQ–TPA, composed of quinoxaline‐5,8‐dicarbonitrile (pCNQ) acceptor and triphenylamine (TPA) donor. pCNQ–TPA supported its OLED with desired CIE coordinates of (0.69, 0.31) and the record maximum external quantum efficiency of 30.3 %, which is the best red TADF diode with Rec.2020 gamut for UHDTV. It is showed that through tuning pCNQ–TPA doping concentration, intra‐ and inter‐molecular charge transfer are balanced to synchronously improve emission color saturation and TADF radiation, and remedy aggregation‐induced quenching, rendering photoluminescence quantum yield (PLQY) reaching 90 % for deep‐red emission peaked at ≈690 nm. Quasi‐planar structure further endows pCNQ–TPA with an improved horizontal ratio of emitting dipole orientation, which increases light out‐coupling ratio to 0.34 for achieving the state‐of‐the‐art device efficiencies. A deep‐red TADF emitter pCNQ–TPA for UHD display was demonstrated, which realized the desired chromaticity matching rec.2020 standard and the record external quantum efficiency beyond 30 %. It is showed that its quasi‐planar structure not only improves horizontal ratio of emitting dipole orientation for out‐coupling enhancement, but also balances the intra‐ and inter‐molecular charge transfer for radiation facilitation and quenching suppression.