As one of the three primary colors, red organic light-emitting diodes (OLEDs) are indispensable in practical applications. However, red emitters are generally subject to severe non-radiative exciton loss due to their narrow energy gap. In this work, three new thermally activated delayed fluorescence (TADF) emitters were developed, namely 4-(acenaphtho[1,2-b]quinoxalin-9-yl)-N,N-diphenylaniline (TPA-AP), 4-(acenaphtho[1,2-b]pyrido[2,3-e]pyrazin-10-yl)-N,N-diphenylaniline (TPA-APy), and 4-(acenaphtho[1,2-b]pyrazino[2,3-e]pyrazin-9-yl)-N,N-diphenylaniline (TPA-APm), employing a series of finely modified acenaphtho[1,2-b]quinoxaline (AP) derivatives as acceptor units. Among three TADF emitters, an intramolecular hydrogen bond is formed between the donor (D) and acceptor (A) units in TPA-APm. Consequently, the overlap of the frontier molecular orbitals (FMOs) of TPA-APm can increase appropriately, and the fluorescence radiative rate (kF) of TPA-APm is nearly twofold than that of TPA-AP and TPA-APy. Furthermore, the non-radiative decay rate (knr) of TPA-APm is less than that of TPA-AP and TPA-APy by an order of magnitude, which is attributed to the improved molecular rigidity caused by intramolecular hydrogen bond. As a result, TPA-APm-based OLEDs achieved a multiplied external quantum efficiency (EQE) of 21.1% with the electroluminescence peak at 590 nm, comparing to only 7.0% and 11.5% for the TPA-AP-based and TPA-APy-based devices, respectively. These results demonstrate appropriate intramolecular hydrogen bond can suppress the influence of non-radiative decay by simultaneously enhancing molecular rigidity and facilitating the fluorescence process, and have great potential in the design of efficient red TADF emitters.