Abstract: To investigate the solution-loss reaction characteristics of cokes with Ca/Fe additives in hydrogen-rich blast furnace, the solution-loss reactions of cokes were carried out by CO2 (N2) carrying H2O vapor with different percentages (0%~30%), and the influence of Ca/Fe additive on the Boudouard reaction (C+CO2=2CO) and water gas reaction (C+H2O=CO+H2) of cokes in H2O@CO2 atmosphere was studied by analyzing the content of CO and H2 in the off gas. The results show that the coke reactivity has a linear relationship with the H2O content in H2O@CO2 and H2O@N2 atmospheres, and the fitting slope k for the solution-loss reaction of coke in H2O@CO2 atmosphere is smaller than that the k value in H2O@N2 atmosphere, which indicates that there is a competition between the reaction of H2O and CO2 and coke in H2O@CO2 atmosphere. Moreover, the difference between the experimental and theoretical reactivities of the basic coke (BC) is less than those of the cokes with Ca/Fe additives (BC+Ca, BC+Fe), which indicates that the Ca/Fe additives have an effect on the competitive relationship of the reactions of CO2 and H2O with coke. The inhibition factors αCO2/H2O and αH2O/CO2 based on the difference of the fitting slope k are proposed to evaluate the degree of inhibition. αCO2/H2O of BC, BC+Fe and BC+Ca cokes are 0.260, 0.251 and 0.170, and αH2O/CO2 of BC, BC+Fe and BC+Ca are 0.121, 0.217 and 0.263. Ca/Fe additives decrease αCO2/H2O and increase αH2O/CO2, indicating that Ca/Fe additives can attenuate the inhibition degree of CO2 on C+H2O reaction and enhance the activity of C+H2O reaction. The catalytically active substances in Ca/Fe additives in cokes are Fe oxide and silicon aluminum calcium salt, and the existence states of Ca/Fe elements in cokes bring about the difference of catalytic effect of Ca/Fe additives on the solution-loss reactions of cokes.