Several coronenes containing pyridine and azaborine units have been readily prepared and structurally confirmed by X-ray crystallographic analysis. The codoping results in interesting findings and properties such as the first observation of BN-H---NPy hydrogen bonds in crystals of BN-PAHs, short π-π stacking distances, lowered HOMO-LUMO levels, narrow band gap, and unique dual response to fluoride ion and proton in solution.