The effects of solute carbon atoms on the thermal expansion coefficients of ferrite and austenite as well as austenitization behavior were investigated by comparing carbon-free ferrite and carbon-containing ferrite. The thermal expansion coefficients and austenitization start and finish temperatures were measured using a dilatometer. Solute carbon atoms at elevated temperatures above the cementite dissolution temperature (650 K) decreased the thermal expansion coefficients of both ferrite and austenite. In addition, minute amount of carbon atoms dissolved in ferrite stimulated austenite nucleation during continuous heating, resulting in the lower starting temperature of austenitization.