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Silicon‐based materials are regarded as the most promising negative electrode materials for next‐generation high‐energy lithium ion batteries due to their high theoretical capacity, low lithiation plateau and low cost, but they still suffer from dramatic volume variation during charge/discharge and sluggish kinetics, substantially restricting their practical applications. Recently, 2D MXenes are demonstrated to improve the electrochemical performances of Si‐based materials owing to their metallic conductivity, large surface aspect ratio, rich surface chemistry, good mechanical strength, etc. Serving as conductive host, MXenes can alleviate the volume expansion of Si during lithiation, enhance the electronic conductivity of the composite and facilitate the electron/ion transport, thus making the resultant Si/MXene composites exhibit excellent performance as negative electrodes of secondary batteries. Herein, an overview toward the recent advances of Si/MXene nanocomposites is presented for lithium storage applications. The preparation strategies and structural characteristics of the Si/MXene nanocomposites are introduced. The applications of diverse Si/MXene nanostructures such as powders, 3D architectures, films and fibers, in lithium ion batteries with corresponding structure‐performance relationships are discussed. Finally, the challenges and perspectives for the future research of Si/MXene nanocomposites are highlighted, aiming to provide a fundamental reference in designing advanced Si/MXene nanocomposites for high‐energy lithium ion batteries. [ABSTRACT FROM AUTHOR]