The development of orange‐red/red thermally activated delayed fluorescence (TADF) materials with both high emission efficiencies and short lifetimes is highly desirable for electroluminescence (EL) applications, but remains a formidable challenge owing to the strict molecular design principles. Herein, two new orange‐red/red TADF emitters, namely AC‐PCNCF3 and TAC‐PCNCF3, composed of pyridine‐3,5‐dicarbonitrile‐derived electron‐acceptor (PCNCF3) and acridine electron‐donors (AC/TAC) are developed. These emitters in doped films exhibit excellent photophysical properties, including high photoluminescence quantum yields of up to 0.91, tiny singlet‐triplet energy gaps of 0.01 eV, and ultrashort TADF lifetimes of less than 1 µs. The TADF‐organic light‐emitting diodes employing the AC‐PCNCF3 as emitter achieve orange‐red and red EL with high external quantum efficiencies of up to 25.0% and nearly 20% at doping concentrations of 5 and 40 wt%, respectively, both accompanied by well‐suppressed efficiency roll‐offs. This work provides an efficient molecular design strategy for developing high‐performance red TADF materials. In this work, orange‐red/red thermally activated delayed fluorescence materials achieve high photoluminescence quantum yields of up to 91% with ultrashort exciton lifetimes of less than 1 µs, demonstrating a successful balance between high efficiency and fast reverse intersystem crossing. Highly efficient organic light‐emitting diodes are realized with external quantum efficiencies of up to 25.0% and small efficiency roll‐offs.