The structural evolution of GaN films during the initial growth process of metalorganic chemical vapor deposition (MOCVD) - low temperature nucleation layer growth, annealing, and high temperature epitaxial growth - was investigated in a synchrotron x-ray scattering experiment. The nucleation layer grown at 560°C that was predominantly cubic GaN consisted of tensile-strained aligned domains and relaxed misaligned domains. The hexagonal GaN, transformed from the cubic GaN during annealing to 1100°C, showed disordered stacking. The atomic layer spacing decreased as the fraction of the hexagonal domains increased. Subsequent growth of epitaxial GaN at 1100°C resulted in the formation of ordered hexagonal GaN domains with rather broad mosaicity.