Reported herein is a molecular design strategy of deep‐blue emitters for resolving the lack of highly efficient deep‐blue organic light‐emitting diodes (OLEDs) featuring CIEy (Commission Internationale de l'Eclairage) color coordinates matching the display requirements (<0.1). The strategy is to combine weak spiro‐donor and spiro‐acceptor groups into a linear donor‐π‐acceptor type of thermally‐activated delayed fluorescence molecule through a sterically bulky π‐spacer. The strategy endows an emitter with deep‐blue emission, a narrower emission bandwidth (51 nm in toluene), a high photoluminescence quantum yield (0.95 in toluene), weak concentration quenching, and efficient triplet‐exciton utilization, which are all attractive characteristics for emitters of deep‐blue OLEDs with lower CIEy coordinates. Owing to the rational design, the emitter has realized not only highly efficient doped deep‐blue OLEDs with external quantum efficiencies (EQEs) up to 25.4 % and CIEy less than 0.1 but also so far the most efficient nondoped deep‐blue OLED (EQE up to 22.5 %) with CIEy less than 0.1.