Optical techniques have been intensively developed for many decades in terms of both experimental and modeling capabilities. In spectroscopy and scatterometry material structures can be measured and modeled from the atomic (binding configurations, electronic band structure) through nanometer (nanocrystals, long range order) to micron scales (photonic structures, gratings, critical dimension measurements). Using optical techniques, atomic scale structures, morphology, crystallinity, doping and a range of other properties that can be related to the changes of the electronic band structure can most sensitively be measured for materials having interband transition energies in the optical photon energy range. This will be demonstrated by different models for the dielectric function of ZnO, a key material in optoelectronics and in numerous other fields. Using polarimetry such as spectroscopic ellipsometry, sub-nanometer precision has long been revealed for the thickness of optical quality layers. The lateral resolution of spectroscopic ellipsometry is limited (> 50 μm) by the use of incoherent light sources, but using single-wavelength imaging ellipsometry, a sub-micron lateral resolution can be reached. In case of sub-wavelength structures, the morphology (of e.g. porous or nanocrystalline materials) can be characterized using the effective medium theory. For structure sizes comparable to the wavelength, scatterometry is applied in a broad versatility of configurations from specular to angle resolved, from coherent to incoherent, from monochromatic to spectroscopic, from reectometric to polarimetric. In this work, we also present an application of coherent Fourier scatterometry for the characterization of periodic lateral structures.