<111>-β-SiC epilayers were prepared on <0001>-α(4H)-SiC by laser chemical vapor deposition at temperatures of 1390–1505 K. Non-explosive and non-corrosive precursor (Hexamethyldisilane, HMDS, Si(CH3)3–Si(CH3)3) was used in non-H2 (Ar) atmosphere. The β-SiC films grew epitaxially with in-plane orientation relationship of β-SiC []//α(4H)-SiC [1000] and β-SiC []//α(4H)-SiC [0100]. The deposition rates of the β-SiC films were 31–261 μm h−1, which were significantly higher than those of conventional CVDs.