Electrochemical exfoliation of graphene is an environmentally friendly method, which enables mass production. Herein, three ionic liquids (ILs) with the same imidazole cation were used to exfoliate graphite into functionalized graphene, as a lubricant additive in an acetonitrile solution. Chemical and structural characterization revealed the relationship between the functionalization density of graphene and the concentration of IL, showing higher concentrations with higher densities. The exfoliated graphene hybrid oil displayed good dispersion because of a high functionalization density. More importantly, the different anions affected the tribological properties of the exfoliated graphene. Among them, the exfoliated graphene with 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIm][PF6]) possessed the best tribological performance, and the average friction coefficient and wear volume were reduced by 32% and 39%, respectively. Through the characterization of worn surfaces and wear debris, the lubrication mechanism and structural evolution of the functionalized graphene were illustrated in detail. The good lubrication function was attributed to the formation of a tribo-film and the disorder transformation of the graphene structure. The simultaneous exfoliation and functionalization of graphene offers a promising advanced lubricant for industrial fabrication.