With the further development of BN-PAHs chemistry by advances in synthetic methodology and by the application potential of BN-doped π-conjugated systems, attention to the structure-property relationship has arisen. The location of BN unit was found to be important to the optoelectronic properties because its location can change whether BN unit could fully conjugate with PAHs. Although both the number of BN unit 8 and different orientations of BN units 9 are believed to exhibit non-negligible impact on the optoelectronic properties and intermolecular interactions, only a few of examples have been documented due to the limited synthetic methodology.