Chemically doping heteroatoms into aromatic compounds has proven to be one of the most effective methods to tune their optoelectronic properties and intermolecular interactions. Due to the isoelectronic relationship between boron and carbon cation as well as between boron-nitrogen (BN) unit and two carbon atoms (CC) motif, boron becomes an important element that can induce novel and complementary properties. BNdoped aromatic compounds have a long history of evolution since the first example of BN-arene was reported by Alfred Stock in 1926. Much the same to many other topics of chemistry, not much attention was paid until the new millennium. Nowadays, the synthesis of BN-doped arenes has become one of the most popular topics in organic chemistry and material chemistry, and numerous new BN-doped aromatic compounds have been synthesized and demonstrated to have very distinct properties in optoelectronic materials. Representative applications of B-doped polycyclic aromatic hydrocarbons (PAHs) have been demonstrated in organic fieldeffect transistor (OFETs) and organic light emitting diodes (OLEDs). Particularly, since PAHs decorated by para-positioned boron and nitrogen atoms has been reported to show thermally activated delayed fluorescence (TADF) with narrow full-width at half-maximum (FWHM) of emission based on efficient HOMO-LUMO separation by the multiple resonance effect in 2016, BN-doped PAHs have been extensively studied for nextgeneration OLEDs.