In this work, dimethylacetamide (DMAc) was investigated as an electrolyte film-forming additive to improve the cyclic stability of high voltage Lithium-rich layered nickel manganese cobalt oxide (LLO) cathode at room (25°C) and elevated (55°C) temperature. At 0.5C rate, addition of 1% DMAc slightly decreases the initial discharge capacity of LLO from 187 to 179mAhg−1 at room temperature and 255 to 246mAhg−1 at elevated temperature, while significantly improves the capacity retention of LLO from 65.8% to 80.2% after 200 cycles at room temperature and from 21.1% to 66.7% after 150 cycles at elevated temperature. The mechanism of DMAc improving the cyclic stability of LLO was investigated via theoretical calculation and experimental characterizations, which demonstrated that DMAc oxidized preferential to the STD (1.0M LiPF6 in a mixed solvent of ethylene carbonate/ethyl methyl carbonate/diethyl carbonate) electrolyte, generating a thin and uniform film on the LLO surface. This film effectively suppresses the subsequent decomposition of STD electrolyte and further degradation of spinel phase converted from the layered structure of LLO, resulting in improved cyclic stability of LLO at room and elevated temperature.