Usage of highly reactive coke in order to decrease the thermal reserve zone temperature in a blast furnace is considered promising to increase the reaction efficiency in the blast furnace and to decrease the reducing agent rate. In order to develop a new method to produce highly reactive coke by adding a Ca catalyst other than Ca-rich coal, in this paper, firstly the effects of Ca compounds pre-addition to coal on coke qualities were investigated. It was shown that carbonizing the mixture of coal and Ca compounds (CaO, CaCO₃) greatly increased coke reactivity and that it was possible to produce Ca-loaded highly reactive coke with high coke strength by adding 3% of Ca compounds under such conditions as high strength coke was produced. Furthermore, the reaction behavior of Ca-loaded highly reactive coke when mixed with conventional coke in the presence of an alkali was investigated. It was shown that when a mixture of Ca-loaded highly reactive coke and conventional coke was heated in a reaction gas, Ca-loaded coke selectively and preferentially reacted. It was also confirmed that Ca acted as catalyst in the existence of K. This shows that the reactivity of Ca-loaded coke is higher than that of conventional coke in an actual blast furnace whereby coke reactivity is promoted by condensed alkali vapor.