To get a small lattice mismatch substrate for GaN, highly ［001］ oriented LiGaO2 layers were successfully fabricated on (100) βGa2O3 single crystal substrates by vapor transport equilibration (VTE). Xray diffractions indicated that the asfabricated layers by VTE were singlephase. As revealed by scanning electron microscopy (SEM), the morphologies of the layers were influenced by the VTE temperature. It was found that the grain size of the layers enlarged with the increasing of the VTE temperature. Xray diffraction results showed that the layers changed from polycrystalline to single crystalline with the increase of VTE temperature. After annealing processing, color center was introduced into LiGaO2 layers as the absorption spectrum showed, kind of the color centers is determined by the annealing temperature. It was shown that (001) LiGaO2∥(100) βGa2O3 composite substrate for GaNbased epitaxial film could be fabricated by VTE technique at the temperature lower than the melting point of LiGaO2.