LAUSR

BN‐heteroarenes, which employ both boron and nitrogen in aromatic hydrocarbons, have gained great attention in the fields of organic chemistry and materials science. Nevertheless, the extensive studies on BN‐heteroarenes are largely limited to 1,2‐azaborine‐based compounds with B–N covalent bonds, whereas 1,3‐ and 1,4‐BN‐heteroarenes are relatively rare due to their greater challenge in the synthesis. Recently, significant progresses have been achieved in the synthesis and applications of BN‐heteroarenes featuring 1,4‐azaborines, especially driven by their significant potential as multiresonant thermally activated delayed fluorescence (MR‐TADF) materials. Therefore, it is timely to review these advances from the chemistry perspective. This review summarizes the synthetic methods and recent achievements of 1,4‐azaborine‐based BN‐heteroarenes and discusses their unique properties and potential applications of this emerging class of materials, highlighting the value of 1,4‐BN‐heteroarenes beyond MR‐TADF materials. It is hoped that this review would stimulate the conversation and cooperation between chemists who are interested in azaborine chemistry and materials scientists working in the fields of organic optoelectronics, metal catalysis, and carbon‐based nanoscience etc.