Advanced multiresonance-induced thermally activated delayed fluorescence (MR-TADF) materials exhibit exceptional promise for applications in state-of-the-art organic light-emitting diodes (OLEDs) owing to their unique narrowband emissions and high luminescent efficiencies. Despite substantial progress with blue and green MR-TADF materials, the development of pure-red MR-TADF emitters has lagged behind, thereby hindering the advancement toward high-performance ultrahigh-definition OLED displays. Here, we propose an effective approach for designing pure-red MR-TADF molecules based on the integration of secondary electron-donating units and π-skeleton extension into MR cores, which enables not only a redshift of narrowband emission but also an acceleration of reverse intersystem crossing (RISC) rate. The proof-of-the-concept emitter BNTPA showcases a bright and saturated red emission centered at 613 nm with a full-width at half-maximum of 0.14 eV, together with a more than twofold increase in the RISC rate. As a result, TADF OLEDs based on BNTPA achieved a record maximum external quantum efficiency (EQEmax) of up to 35.2% with Commission Internationale de l'Eclairage (CIE) coordinates of (0.657, 0.343), approaching the coordinates of the National Television Standards Committee (NTSC) red standard. Moreover, phosphor-assisted fluorescence devices exploiting BNTPA as a terminal emitter exhibit an exceptional EQEmax of 43.3%, accompanied by improved operational stability.