High quality CuGaSe2 and CuInSe2 single crystalline layers are grown on GaAs (001) by employing the deposition sequence of migration enhanced epitaxy using a solid source molecular beam epitaxy system. When CuGaSe2 is grown on CuInSe2 at moderate temperatures, severe interdiffusion takes place at the heterojunction of CuGaSe2/CuInSe2. This problem has been solved by optimizing the growth temperature and deposition rates of the constituent elements. Thus, we have successfully grown CuGaSe2/CuInSe2 single quantum well with sharp interfaces on GaAs (001) for the first time. Intense photoluminescence from the single quantum well with 10 nm well width is demonstrated. (C) 2015 Elsevier B.V. All rights reserved.