In-situ reflection high-energy electron diffraction (RHEED) observation and X-ray diffraction measurements were performed on heterojunction interfaces of CuGaSe2/CnInSe2/CuGaSe2 grown on GaAs (001) using migration-enhanced epitaxy. The streaky RHEED pattern and persistent RHEED intensity oscillations caused by the alternate deposition of migration-enhanced epitaxy sequence are observed and the growths of smooth surfaces are confirmed. RHEED observation results also confirmed constituent material interdiffusion at the heterointerface. Cross-sectional transmission electron microscopy showed a flat and abrupt heterointerface when the substrate temperature is as low as 400 °C. These have been confirmed even by X-ray diffraction and photoluminescence measurements.