The sp2-bonded layered compound boron nitride (BN) exists in more than a handful of different polytypes (i.e., different layer stacking sequences) with similar formation energies, which makes obtaining a pure monotype of single crystals extremely tricky. The co-existence of polytypes in a similar crystal leads to the formation of many interfaces and structural defects having a deleterious influence on the internal quantum efficiency of the light emission and on charge carrier mobility. However, despite this, lasing operation was reported at 215 nm, which has shifted interest in sp2-bonded BN from basic science laboratories to optoelectronic and electrical device applications. Here, we describe some of the known physical properties of a variety of BN polytypes and their performances for deep ultraviolet emission in the specific case of second harmonic generation of light.