The ability to determine structural and compositional information from the sub‐surface region of a semiconductor material has been demonstrated using a new time‐of‐flight medium energy ion scattering spectroscopy (ToF‐MEISS) system. A series of silicon–silicon/germanium (Si/Si1−xGex) heterostructure and multilayer samples, grown using both solid source molecular beam epitaxy (MBE) and gas source chemical vapor deposition (CVD) on Si(100) substrates, have been investigated. These data indicate that each individual layer of Si1−xGex(x∼0.22) in both two‐ and three‐period samples, can be uniquely identified with a resolution of approximately 3 nm. A comparison of MBE and CVD grown samples has also been made using layers with similar structures and composition. The total Ge content of each sample was confirmed using conventional Rutherford backscattering spectrometry. ©1995 American Institute of Physics.