The excellent theoretical specific charge (lithium) storage capacity and rich abundance of silicon (Si), and the good mechanical and electrical properties of titanium based MXene (Ti3C2T x ) nanosheets promise high performance composites (Si/Ti3C2T x ) for negative electrodes (negatrodes) in future lithium ion battery (LIB) applications. In particular, the Si/Ti3C2T x composites have been preliminarily shown to offer large and stable cyclic capacity, good rate capability and a highly profitable market prospect. To better understand and help further improve the electrochemical performance of these composites, this review focuses on the electrochemical processes occurring in Si/MXene composites from a material perspective. Different cells used for electrochemical measurements, the related materials properties and the reaction processes and kinetics of Si/MXene composites as negatrode in LIB are reviewed. The perspective is also discussed for practical applications in flexible electronic devices and automobiles.