The paper presents a novel process for synthesis of ultrafine titanium carbide by reaction between TiOSO4 and Phenol-formaldehyde resins at different temperatures in the range of 1450°C–1500°C under argon cover for 1 hr. It was a new low-cost synthetic route for fabricating ultrafine TiC powders. The thermodynamic and reaction processes about phenolic resin’s cracking and reducing in the system of titanium oxide were studied. When the organic cracking reaction ended at 1000°C, amorphous carbon was provided by phenolic resin’s cracking. The grain size distribution of TiC synthesized from organic carbon was more narrower than that from inorganic carbon.