This article reviews the use of spectroscopic ellipsometry (SE) for determining layer thicknesses, compositions, and surface and interface roughness of complex multilayer structures. An indirect technique, SE relies on an accurate database of dielectric functions and cross-correlation with destructive techniques. Examples shown here use recent data on strained and relaxed Si 1 _ x Ge x ,strained and relaxed In,Ga 1 _,As, and unstrained In,All_,As, obtained from single epilayers, to analyze SE data from both lattice-matched and pseudomorphic multi/ayer structures. The SE method has great potential for in-line and in-situ use, leading ultimately to realtime process control.