Polycyclic aromatic hydrocarbons are widely used in optoelectronic materials, and heteroatom doping can effectively modulate the physicochemical properties of polycyclic aromatic hydrocarbons. Boron nitrogen (BN)-doped aromatics are important members of polycyclic aromatic hydrocarbons (PAHs) family. Based on the relative positions of boron and nitrogen atoms, BN-doped aromatics can be divided into three forms: 1,2-BN heteroaromatics, 1,3-BN heteroaromatics and 1,4-BN heteroaromatics. Despite the blooming researh of 1,2-BN heteroaromatics, the 1,3- and 1,4-BN heteroaromatics were much less studied. Owing to recent advances in multi-resonance thermally acitvated fluoresence (MR-TADF) materials based on 1,4-BN heteroaromatics, the research of 1,4-BN-heteroaromatics is currently ondergoing a renassiance. In particular, researchers from China have actively participated in and promoted the rapid development of 1,4-BN heteroaromatics, and the large number of recent publications also demonstrate the remarkable growth of the MR-TADF material based on 1,4-BN heteroaromatics. Taking the structure of 1,4-BN heteroaromatics as a clue, the synthesis and development history of 1,4-BN heteroaromatics are reviewed based on the heteroatom binary doping (B/N) framework and ternary doping (X/B/N) framework. Finally, the future development and application of 1,4-BN heteroaromatics are prospected.