The electrolytes based on lithium oxalyldifluoroborate (LiODFB) and carbonates have been systematically investigated for LiFePO4/artificial graphite (AG) cells, by ionic conductivity test and various electrochemical tests, such as cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and charge–discharge test. The conductivity of nine electrolytes as a function of solvent composition and LiODFB salt concentration has been studied. The coulombic efficiency of LiFePO4/Li and AG/Li half cells with these electrolytes have also been compared. The results show that 1M LiODFB EC/PC/DMC (1:1:3, v/v) electrolyte has a relatively higher conductivity (8.25mScm−1) at 25°C, with high coulombic efficiency, good kinetics characteristics and low interface resistance. With 1M LiODFB EC/PC/DMC (1:1:3, v/v) electrolyte, LiFePO4/AG cells exhibit excellent capacity retention ∼92% and ∼88% after 100 cycles at 25°C and at elevated temperatures up to 65°C, respectively; The LiFePO4/AG cells also have good rate capability, the discharge capacity is 324.8mAh at 4C, which is about 89% of the discharge capacity at 0.5C. However, at −10°C, the capacity is relatively lower. Compared with 1M LiPF6 EC/PC/DMC (1:1:3, v/v), LiFePO4/AG cells with 1M LiODFB EC/PC/DMC (1:1:3, v/v) exhibited better capacity utilization at both room temperature and 65°C. The capacity retention of the cells with LiODFB-based electrolyte was much higher than that of LiPF6-based electrolyte at 65°C, while the capacity retention and the rate capacity of the cells is closed to that of LiPF6-based electrolyte at 25°C. In summary, 1M LiODFB EC/PC/DMC (1:1:3, v/v) is a promising electrolyte for LiFePO4/AG cells.