We report epitaxial growth of GaN layers on z ‐ and x ‐cut LiNbO3 substrates using MOVPE. GaN layers with the thickness of 450 nm were characterized using X‐ray diffraction. For both, z‐ and x‐ cut orientations of LiNbO3 substrates, the GaN layers have c‐axis orientation normal to the substrate plane and the in‐plane lattice orientation of GaN layers coincides with the primary axes of LiNbO3 substrates. Although GaN layers exhibit almost complete strain relaxation, the residual compressive strain determined with respect to a free‐standing GaN is of the order of +0.37% and +0.2% for z ‐ and x ‐cut substrates, respectively. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)