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 (Ti3C2Tx) nanosheets promise high performance composites (Si/Ti3C2Tx) for negative electrodes (negatrodes) in future lithium ion battery (LIB) applications. In particular, the Si/Ti3C2Tx 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.