Variable angle spectroscopie ellipsometry (VASE), a nondestructive optical technique, was used to characterize two different multilayer samples, each having a low-pressure chemical vapor deposited polycrystalline silicon (poly-Si) layer. Analysis of these samples by cross-sectional transmission electron microscopy (XTEM) revealed large changes in grain size, between the undoped, as-deposited, and doped, annealed poly-Si layers. Roughness at the top of the poly-Si layers was also observed by XTEM. These features, together with the other structure parameters (thickness and composition), were analyzed ellipsometrically by fitting the measured VASE spectra with appropriate multilayer models. Each composite layer (surface overlayer, interfacial layer, and poly-Si layer) was modeled as a physical mixture, using the Bruggeman effective medium approximation. The ellipsometrically determined thicknesses were in very good agreement with the corresponding results measured by XTEM. Furthermore, VASE analysis provided additional information about the relative fractions of the constituent materials in the different composite layers. Thus, it quantitatively characterized the surface and interracial properties, and also the doping and annealing effects on the microstructure of poly-Si layers.