This article reports conversion chemistry of preceramic polymer to ceramic phase during the fabrication of high-temperature stable silicon carbide and silicon carbonitride monolithic porous microchannels. The micromolding in capillariesmethod is used to fabricate porous channels by the initial infiltration of a solution of 1.5-μm diameter silica spheres or 1-μm diameter polystyrene spheres into polydimethylsiloxane channels followed by filling the void space among the spheres by using viscous commercial polymeric precursors. Subsequently, the polymer-sphere composite channel was cured and pyrolysed at 1200 °C under inert atmosphere, and final wet etching step of silica spheres with 10% hydrofluoric acid solution developed the pore structures by removing the silica spheres, whereas polystyrene sphere decomposes at the early stage of pyrolysis.