Lithium difluoro(oxalato)borate (LiDFOB) with one oxalate moiety bonded to a central boron core was employed as a salt-type additive to enhance the interfacial stabilities of high-voltage Li-rich cathodes and graphite anodes. Our investigation revealed that the LiDFOB additive modified the surface film on the electrodes and effectively restrained degradation of the cycling performance of the electrodes. Investigation of the surface chemistries of the electrodes confirmed that LiDFOB produces a LiF-less surface film on the Li-rich cathode and a LiF-rich surface film on the graphite anode. Moreover, the use of 1% LiDFOB drastically improved the rate capabilities of Li-rich cathodes and graphite anodes. Within 100 cycles at a rate of C/2 at 25 °C, only 45.8% of the initial discharge capacity of a high-voltage Li-rich/graphite full cell was delivered in the baseline electrolyte, while the LiDFOB-containing electrolyte retained 82.7%.