The ternary [Li+]0.09[MePrPyr+]0.41[NTf2 −]0.50 room temperature ionic liquid was obtained by dissolution of solid lithium bis(trifluoromethanesulfonyl)imide (LiNTf2) in liquid N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([MePrPyr+][NTf2 −]), and studied as an electrolyte for lithium-ion batteries. The graphite–lithium (C6Li) anode, working together with vinylene carbonate as an additive showed ca. 90% of its initial discharge capacity after 50 cycles. The addition of vinylene carbonate to the neat ionic liquid results in the formation of the protective coating (SEI) on both the lithium and graphite anodes. The SEI formation increases the rate of the charge transfer reaction as well as protects the anode from chemical passivation (corrosion). The graphite–lithium (C6Li) anode shows good cyclability and Coulombic efficiency in the presence of 10wt.% of vinylene carbonate as an additive to the ionic liquid.