Polymer derived ceramic composites have been developed for SOFC seals. The formation and properties of the ceramic composite derived from a mixture with polysiloxane and filler were investigated. In the presence of filler materials such as ZrO2 and AlCo, the thermal properties of the ceramic composite could be controlled. The mixtures with polymethylsiloxane and fillers were prepared and their conversions to ceramic composites by annealing in N2 atmosphere were studied. The microcrystalline composites with filler embedded in a silicon-boron-oxycarbide glass matrix were formed. The thermal expansion behaviors were measured and discussed.