In this study, Si nanoparticles with interweaving carbon nanotubes are wrapped by graphitic sheets to achieve high conductivity and high dimensional stability of a composite anode (denoted as Si/CNT/G) for Li-ion batteries. In addition, an ionic liquid (IL) electrolyte that consists of ether-side-chain pyrrolidinium, asymmetric imide, and a high Li+ fraction is prepared. This electrolyte is for the first time employed for Si-based Li-ion batteries. Decomposition of the ether groups creates organic components in the solid electrolyte interphase (SEI). The high Li+ concentration promotes decomposition of the (fluorosulfonyl)(trifluoromethanesulfonyl)imide (FTFSI−) anions, leading to a LiF- and Li3N-rich SEI. The organic-inorganic balanced SEI is responsible for the excellent charge-discharge properties of the Si/CNT/G anode. The FTFSI− anions exhibit low corrosivity toward the Al current collector and high compatibility with the LiNi0.8Co0.1Mn0.1O2 (NCM-811) cathode. With a charging voltage of 4.5 V, remarkable reversible capacities and cycling stability of NCM-811 in the high-Li+-fraction N-methoxyethyl-N-methylpyrrolidinium/FTFSI IL electrolyte are observed. Differential scanning calorimetry is used to examine the interfacial exothermic reactions between the delithiated NCM-811 and various electrolytes. After 300 charge-discharge cycles, the capacity retention of a Si/CNT/G||NCM-811 full cell with the proposed IL electrolyte is 80% with a Coulombic efficiency of ∼99.9%. These values are significantly higher than those of the conventional carbonate electrolyte cell.