The electrochemical behaviors of copper current collector in 1-alkyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl] imide ionic liquid electrolytes were investigated and compared with that in ethylene carbonate/dimethyl carbonate solutions. Cyclic voltammetry results showed that large oxidation–reduction current of the copper foil appeared in ethylene carbonate/dimethyl carbonate solutions, while a much smaller current in the room temperature ionic liquid electrolytes decreased gradually, indicating that the copper foil was anodically stable. Further study by X-ray photoelectron spectroscopy analysis showed that an unstable product was composed mainly of the carbonate and carbonyl species on the surface of the copper foil after the electrochemical measurement in ethylene carbonate/dimethyl carbonate solutions, leading to the dissolution of the copper foil. While a better passivating film from the reduction of the anions in the room temperature ionic liquid electrolytes covered the surface of copper foil and protected the copper foil from being oxidized even in a higher potential. These results indicate that the use of room temperature ionic liquid electrolytes can improve the stability of copper current collector in the advanced lithium ion batteries.