Ceramic matrix composites (CMC) were prepared by the active-filler-controlled polymer pyrolysis process (AFCOP) using a polysilsesquioxane resin filled with metallic niobium and alumina powders. Samples containing 60 wt% of polysilsesquioxane and 40 wt% of metallic niobium and alumina powders mixtures were homogenized, uniaxially pressed and pyrolysed in an alumina tube furnace up to 1400 °C, under argon flow. The ceramic products were characterized by X-ray diffraction (XRD), thermogravimetry (TGA), differential thermal analysis (DTA), Fourier transform infrared (FTIR) and energy-dispersive (EDS) spectroscopies. XRD analysis of the products showed the presence of crystalline phases such as NbC, Nb3Si, Nb5Si3, SiC, crystoballite and mullite. Thermogravimetry data of the composites presented low weight losses at 1000 °C. DTA curves showed an endothermic peak at 1350 °C, which was associated to the beginning of carbothermic reduction and/or the formation of silicon oxide and carbide. In addition, an exothermic peak at 1400 °C was associated to the formation of the mullite phase.