The chemically modified polycarbosilane (PC) containing organofluoric groups, PCOCF, was synthesized through chemical reaction of PC and fluoric alcohol. Pyrolysis of the polymer precursor occurred in three stages under 1000 °C. Weight loss due to evaporation of low molecular compounds was observed at the first stage below 300 °C, followed by the largest weight loss from 300 to 600 °C at the second stage. At this stage, side chains formed during the chemical reaction were removed. Finally, side chains such as Si–CH3 decomposed at the third stage above 600 °C. At 1000 °C, the chemical modification of PC resulted in high yield of solid product. After coating PCOCF on silicon carbide (SiC) powders, the conversion yield of pyrolyzed PCOCF was further improved due to the interaction between PCOCF and SiC powders. Coating of PCOCF on SiC powders was found to be effective in increasing the green density of uniaxially pressed bodies.