Active filler controlled pyrolysis of polymers (AFCOP) is a recent method for obtaining near-net shaped ceramic bodies. Alumina based composites have been developed for use as cutting tools, so knowledge of the surface composition is extremely important because it is directly related to the hardness and wear resistance Samples containing a fixed concentration of 60 wt. (%) of polysiloxane and a mixture of metallic niobium and alumina powder were homogenized, uniaxially warm pressed at 80 °C and subsequently pyrolyzed in flowing argon at 1200, 1400 and 1500 °C. Analysis of the surface composition was carried out by X ray photoelectron spectroscopy, infrared spectroscopy, X ray diffraction and scanning electron microscopy. The results have indicated that the formation of the phases on the surface depends strongly on the niobium/carbon ratio in the raw materials.