The electrochemical mechanism of the reaction between Fe-C melts and CaO-SiO2-Al2O3-FeOx slag systems has been carried out. The experimental results suggest that the final content of carbon in melt increases as the partial oxygen pressure of gas decreases no matter whether there is electronic conductor or not. However, the final content of carbon in the system with electronic conductor is much lower than that without electronic conductor. It can be deduced that the transfer ability of oxygen in slag is dominated by electrons. When an electronic conductor exists, an easy pathway for the electrons is provided and the oxygen transfer rate is accelerated.