Measurements of the grain boundary character distribution in MgAl2O4 (spinel) as a function of lattice misorientation and boundary plane orientation show that at all misorientations, grain boundaries are most frequently terminated on {111} planes. Boundaries with {111} orientations are observed 2.5 times more frequently than boundaries with {100} orientations. Furthermore, the most common boundary type is the twist boundary formed by a 60degrees rotation about the [111] axis. {111} planes also dominate the external form of spinel crystals found in natural settings, and this suggests that they are low energy and/or slow growing planes. The mechanisms that might lead to a high population of these planes during solid state crystal growth are discussed.