Highly (0 0 1) orientation LiGaO 2 layers have been successfully fabricated on (1 0 0) β-Ga 2 O 3 surface by vapor transport equilibration (VTE) technique. The temperature is very important for the VTE treatment. At low temperature (800°C), LiGaO 2 layers are textured. As the temperature was raised to 1100°C the layer becomes highly oriented in the [1 0 0] direction. It shows that the best temperature for VTE treatment is 1100°C. This technique is promising to fabricate small lattice mismatch composite substrate of LiGaO 2 (0 0 1)β-Ga 2 O 3 (100) for GaN films.