Two series of BN-phenanthrenes, including the parental compounds, have been synthesized in an efficient manner from commercially available materials. Both parental BN-phenanthrenes are strongly fluorescent in solution. Their absorption and emission spectra are greatly dependent on the BN position and orientation. Moreover, the reactivities of the two series of BN-phenanthrenes toward electrophiles are completely different, and these species can be further functionalized by cross-coupling reactions.