© 2021 John Wiley & Sons Ltd.In this work, as an alternative to the silicon-based anodes, Li22Si5/rGO composite electrodes were synthesized and their electrochemical performances were investigated by the electrochemical impedance spectroscopy, cyclic voltammetry, and charge/discharge tests. The effects of rGO and PVDF contents on the performance of the composite electrodes were also observed. Although the composite electrodes with the low PVDF content exhibited a high discharge capacity, their cyclic performances were very poor. The excess amount of PVDF content, however, even in the presence of high rGO content, caused the charge transfer resistance and the discharge capacity irreversibility to increase in the composite electrodes. The composite electrode with 70% Li22Si5 alloy, 15% rGO, and 15% PVDF (LSRGO15) contents exhibited the best electrode performance in this work. The LSRGO15 electrode had 822 mA h g−1 discharge capacity at the 100th cycle. These performance values demonstrated that Li22Si5/rGO composite electrodes were highly promising as the alternative anode materials for the LIBs.