We report on the application of infrared spectroscopic ellipsometry (IR-SE) for wavenumbers from 333cm−1 to 1200cm−1 as a novel approach to non-destructive optical characterization of free-carrier and optical phonon properties of group III-nitride heterostructures. Undoped α-GaN, α-AlN, α-Al
N (x = 0.17, 0.28, 0.5), and n-type silicon (Si) doped α-GaN layers were grown by metal-organic vapor phase epitaxy (MOVPE) on c-plane sapphire (α-Al2O3). The four-parameter semi-quantum (FPSQ) dielectric lattice-dispersion model and the Drude model for free-carrier response are employed for analysis of the IR-SE data. Model calculations for the ordinary (∈
⊥) and extraordinary (∈
||) dielectric functions of the heterostructure components provide sensitivity to IR-active phonon frequencies and free-carrier parameters. We observe that the α-Al
N layers are unintentionally doped with a back ground free-carrier concentration of 1–4 1018cm−3. The ternary compounds reveal a two-mode behavior in ∈⊥, whereas a one-mode behavior is sufficient to explain the optical response for ∈||. We further provide a precise set of model parameters for calculation of the sapphire infrared dielectric functions which are prerequisites for analysis of infrared spectra of III-nitride heterostructures grown on α-Al2O3.