As a high-potential and high-stability cathode material, LiVPO4F/C is modified by K+ and Zr4+ co-doping to significantly improve its high-rate and long-life performance. K+ assisted by Zr4+ slightly enlarges the unit cell volume to expand Li+ migration pathway. K+ substituting Li+ can also achieve pillar effect to increase the structural stability. Hall effect reveals that Zr4+ substituting V3+ is a donor doping, leading to the transformation of conductive type from p-type to n-type and a great increase of carrier density by 106 times. Therefore, the electronic conductivity (1.1 × 10−2 S cm−1) increases by a factor of ∼104. The charge transfer resistance decreases to 82.81 Ω and the Li+ diffusion coefficient (9.83 × 10−13 cm2 s−1) increases to 7 times that of undoped LiVPO4F/C. The discharge capacities of Li0.99K0.01V0.995Zr0.005PO4F/C at 0.1C and 1C are 143.3 mA h g-1 and 135.5 mA h g-1, respectively. The capacity retention at the charge/discharge rate of 10C is as high as 80.0% after 2000 cycles with an initial capacity of 108.1 mA h g-1. Even at the discharge rate of 60C (charging at 1C), the capacity reaches 105.7 mA h g-1.