Although the total amount of boron resources in China is high, the grades of these resources are low. The authors have already proposed a new comprehensive utilization process of boron-bearing iron concentrate based on the iron nugget process. The present work describes a further optimization of the conditions used in the previous study. The effects of CaO on the reduction–melting behavior and properties of the boron-rich slag are presented. CaO improved the reduction of boron-bearing iron concentrate/carbon composite pellets when its content was less than 1wt%. Melting separation of the composite pellets became difficult with the CaO content increased. The sulfur content of the iron nugget gradually decreased from 0.16wt% to 0.046wt% as the CaO content of the pellets increased from 1wt% to 5wt%. CaO negatively affected the iron yield and boron extraction efficiency of the boron-rich slag. The mineral phase evolution of the boron-rich slag during the reduction–melting separation of the composite pellets with added CaO was also deduced.