The thermal alteration process of filmy quenched carbonaceous composite (filmy QCC) has been studied in situ by high-resolution transmission electron microscopy (HRTEM). HRTEM images of the as-prepared filmy QCC showed the typical amorphous carbon film structure. By heating above 300 °C, the structural alteration takes place. Curled graphene structure started to appear at 300 °C. Distorted onion-like structure similar to dark QCC appeared above 500 to 700 °C. The distorted onion-like structure that appears at 700 °C after heating for 30 minutes also appeared by heating at 450 °C for 2 hours.