Silicon–graphite (Si@G) anodes are receiving increasing attention because the incorporation of Si enables lithium-ion batteries to reach higher energy density. However, Si suffers from structure rupture due to huge volume changes (ca. 300%). The main challenge for silicon-based anodes is improving their long-term cyclabilities and enabling their charge at fast rates. In this work, we investigate the performance of Si@G composite anode, containing 30 wt.% Si, coupled with a LiNi0.8Co0.15Al0.05O2 (NCA) cathode in a pouch cell configuration. To the best of our knowledge, this is the first report on an NCA/Si@G pouch cell cycled at the 5C rate that delivers specific capacity values of 87 mAh g−1. Several techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and gas chromatography–mass spectrometry (GC–MS) are used to elucidate whether the electrodes and electrolyte suffer irreversible damage when a high C-rate cycling regime is applied, revealing that, in this case, electrode and electrolyte degradation is negligible.