LiInSe2films were grown on GaP substrates using a hot wall technique. Reflection high‐energy electron diffraction analysis showed that LiInSe2, having a &bgr;‐NaFeO2(wurtzitelike) structure, grows epitaxially on a ⟨111⟩Aoriented GaP at substrate temperatures ranging from 360 to 400 °C and at the wall temperature of 650 °C with the compensation of Se. The crystalline quality of the epitaxial layers on substrates was investigated by Rutherford backscattering (RBS). The depth profile of RBS‐aligned spectrum showed the relative low minimum yield of backscattered particles except for that near the interface. Auger electron spectroscopy measurements showed that the atomic concentration ratio of Se and In in films was 2.