AbstractIron fluoride, an intercalation-conversion cathode for lithium ion batteries, promises a high theoretical energy density of 1922 Wh kg^–1_. However, poor electrochemical reversibility due to repeated breaking/reformation of metal fluoride bonds poses a grand challenge for its practical application. Here we report that both a high reversibility over 1000 cycles and a high capacity of 420 mAh g⁻¹ can be realized by concerted doping of cobalt and oxygen into iron fluoride. In the doped nanorods, an energy density of ~1000 Wh kg⁻¹ with a decay rate of 0.03% per cycle is achieved. The anion’s and cation’s co-substitutions thermodynamically reduce conversion reaction potential and shift the reaction from less-reversible intercalation-conversion reaction in iron fluoride to a highly reversible intercalation-extrusion reaction in doped material. The co-substitution strategy to tune the thermodynamic features of the reactions could be extended to other high energy conversion materials for improved performance.