Thin composite films made from a thermally stable hyperbranched polyphenylene and a thermolabile hyperbranched polycarbonate were prepared on silicon wafers and characterised. The end groups of the polycarbonate were varied in order to accomplish an optimised interaction between the two components and thus the formation of homogeneous blends. The composite films were annealed at 200 degrees C in order to decompose the hyperbranched polycarbonate which can act as a porogen. The composition of the films before and after the annealing process was investigated applying IR spectroscopy and spectroscopic ellipsometry. Analysis of the data allowed calculating the volume fractions of the two materials within the films.