Spectroscopic ellipsometry (SE) has been used for the characterization of AlGaN/GaN and InGaN/GaN heterostructures. The resulting pseudodielectric function spectra were analyzed using a multilayer approach, describing the dielectric functions of the individual layers by a parametric oscillator model. From this analysis, the dielectric function spectra of GaN, AlxGa1−xN (x≤0.16), and In0.13Ga0.87N were deduced. Further, the dependence of the AlxGa1−xN band gap energy on the Al mole fraction was derived and compared with photoluminescence data recorded on the same material. The SE band gap data are compatible with a bowing parameter close to 1 eV for the composition dependence of the AlxGa1−xN gap energy. Finally, the parametric dielectric functions have been used to model the pseudodielectric function spectrum of a complete GaN/AlGaN/InGaN LED structure.