Structural characterization technique of hetero-interfaces using surface-sensitive EXAFS is reviewed. Principles and experimental techniques are briefly described. Results of application to structural studies of Si/Ge/Si (100) hetero-interfaces perepared by molecular beam epitaxy (MBE) are reported. The formation of ordered Si/Ge/Si interface is evidenced by Fourier transform analysis of Ge K-EXAFS oscillations. Future prospects for in-situ stuctural analysis of epitaxially-grown semiconductor interfaces using a high brilliance synchrotron radiation are discussed.