We report the growth of GaN films on the Si(1 1 1) substrate by metalorganic chemical vapour phase deposition (MOCVD). Different buffer layers were used to investigate their effects on the structural and optical properties of GaN layers. A series of GaN layers were grown on Si(1 1 1) with different buffer layers and buffer thicknesses and were characterized by Nomarski microscopy, atomic force microscopy, high-resolution x-ray diffraction (XRD) and photoluminescence (PL) measurements. We first discuss the optimization of the LT-AlN/HT-AlN/Si(1 1 1) templates and then the optimization of the graded AlGaN intermediate layers. In order to prevent stress relaxation, step-graded AlGaN layers were introduced along with a crack-free GaN layer of thickness exceeding 2.6 νm. The XRD and PL measurements results confirmed that a wurtzite GaN was successfully grown. The resulting GaN film surfaces were flat, mirror-like and crack-free. The mosaic structure in the GaN layers was investigated. With a combination of Williamson-Hall measurements and the fitting of twist angles, it was found that the buffer thickness determines the lateral coherence length, vertical coherence length, as well as the tilt and twist of the mosaic blocks in GaN films. The PL spectra at 8 K show that a strong band edge photoluminescence of GaN on Si (1 1 1) emits light at an energy of 3.449 eV with a full width at half maximum (FWHM) of approximately 16 meV. At room temperature, the peak position and FWHM of this emission become 3.390 eV and 58 meV, respectively. The origin of this peak was attributed to the neutral donor bound exciton. It was found that the optimized total thickness of the AlN and graded AlGaN layers played a very important role in the improvement of quality and in turn reduced the cracks during the growth of GaN/Si(1 1 1) epitaxial layers.