Chemically modified polycarbosilane (PC) which contains Si–Al–C–O component, PCOAl, was synthesized using PC and aluminum triisopropoxide. Ceramic yield was greatly improved through the modification of PC with a metal alkoxide. The phase transformation behavior and microstructure development of silicon carbide (SiC) were studied on β–SiC powders coated with chemically modified PC. The β-α phase transformation of SiC was enhanced by the coating of chemically modified PC on β–SiC powder. A unique microstructure with submicron-sized plate-like grains was developed, since the fine a phase produced at low temperature served as a nucleation site for the β-α phase transformation of SiC.