Bismuth fluoride (BiF3) is a promising positive electrode material for fluoride shuttle batteries (FSBs) owing to its high theoretical specific capacity (302mAhg−1). However, it exhibits low practical capacity. The methods for preparing the electrode are known to have significant effects on battery performance. The mixture between BiF3 and carbon, BiF3/C, prepared by high energy ball milling method has been already approved in lithium ion batteries. With this method, a significant improvement over the discharge and charge capacities of the BiF3/C electrode has been achieved. In this work, for the first time, BiF3/C electrode has been used for FSB. Using BiF3/C electrode significantly increased the discharge and charge capacities. To confirm the progress of the discharge and charge reactions of BiF3/C electrode, the crystal structure of active materials and oxidation state of Bi for the BiF3/C electrode during discharging and charging has been investigated by X-ray diffraction and X-ray absorption fine structure. The results reveal that, with higher capacity values, discharge and charge reactions related to BiF3/C have been realized.