Manufacturing of novel reaction bonded Niobium Carbide (NbC) containing ceramic composites derived from polymer/filler mixtures was investigated. Poly(methylsiloxane) filled with 40 vol.% of a mixture of metallic Niobium (Nb) (reactive filler) and alumina powder (inert filler) was pyrolysed in inert atmosphere up to 1450 degrees C. During pyrolysis metallic niobium reacted with carbon from the decomposition products of the preceramic polymer binder to form microcrystalline composites of NbC, Al2O3 and a silicon oxycarbide glass. Microstructure formation of specimens prepared with different niobium to alumina ratio in the starting mixture was experimentally examined and compared to thermodynamic phase equilibria calculations. Materials of high NbC content exhibit high hardness and wear resistance.