We develop and discuss appropriate methods based on x-ray diffraction and generalized infrared spectroscopic ellipsometry to identify wurtizte and zinc-blende polymorphs, and quantify their volume fractions in mixed-phase epitaxial films taking InN as an example. The spectral signatures occurring in the azimuth polarization (Muller matrix) maps of mixed-phase epitaxial InN films are discussed and explained in view of polymorphism (zinc-blende versus wurtzite), volume fraction of different polymorphs and their crystallographic orientation, and azimuth angle. A comprehensive study of the structural, phonon and free electron properties of zinc-blende InN films containing inclusions of wurtzite InN is also presented. Thorough analysis on the formation of the zinc-blende and wurtzite phases is given and the structural evolution with film thickness is discussed in detail. The phonon properties of the two phases are determined and discussed together with the determination of the bulk free-charge carrier concentration, and electron accumulation at the mixed-phase InN film surfaces.