9a,9-BN anthracene was synthesized using a simple three-step sequence involving intramolecular electrophilic borylation of 2-benzylpyridines. The same procedure can be applied to yield a number of substituted 9a,9-BN anthracenes. Spectroscopic characterization of the parental compound (UV-photoelectron spectroscopy, UV-vis absorption/emission) shows an electronic structure more similar to that of a larger conjugated system rather than anthracene, the direct all-carbon analogue.