The (1 0 0) face of γ-LiAlO2 has attracted attention as a possible substrate for GaN epitaxial growth. This is partly because this face has an excellent lattice and structural match to (1 0 0) GaN. This orientation would have a misfit of only −1.4% along the c-direction and −0.1% along the b-direction of LiAlO2. We find that in practice this orientation relationship does not occur; instead, (0 0 0 1) oriented GaN grows with a small tilt (0.6° towards the c-direction) between the film and substrate. Although the misfit along the substrate b direction is large (−6.3%) for this orientation, the tilt perfectly accommodates the −1.4% misfit in the c direction. We present characterization of these films by RHEED, X-ray diffraction, and TEM. We propose that the tilt is driven by a reduction of interface energy which occurs in polar, incoherent interfaces.