Growth of hexagonal GaN on Si(100) templates via pulsed laser deposition (PLD) was investigated for the further development of GaN-on-Si technology. The evolution of the GaN growth mechanism at various growth times was monitored by SEM and TEM, which indicated that the GaN growth mode changes gradually from island growth to layer growth as the growth time increases up to 2 hours. Moreover, the high-temperature operation (1000°C) of the PLD meant no significant GaN meltback occurred on the GaN template surface. The completed GaN templates were subjected to MOCVD treatment to regrow a GaN layer. The results of X-ray diffraction analysis and photoluminescence measurements show not only the reliability of the GaN template, but also the promise of the PLD technique for the development of GaN-on-Si technology.