Despite its high theoretical specific capacity, direct application of SiO[Formula: see text] is challenging particularly in terms of alleviating volume effect and improving electronic conductivity to enhance the battery performance. SiO[Formula: see text]/CNTs/Sn composite with high cyclability and rate performance was proposed by a modified Stöber liquid phase method, CNTs and metallic tin were employed during the subsequent mechanical ball milling process to investigate their effects on the resulting physicochemical property and electrochemical performance. The structure of/CNTs/Sn composite was designed, and the multi-structure not only alleviates the volume effect of SiO[Formula: see text] to a certain extent but also provides additional diffusion pathways for lithium ions, electrons, and flexible substrate. From electrochemical characterization, the half-cell battery integrating SiO[Formula: see text]/CNTs/Sn anode exhibits a capacity of 880.83 mAh g[Formula: see text] with 6.3% capacity fading after 100 cycles at 0.1 A g[Formula: see text] and excellent rate performance. The simple and ingenious synthesis method could provide new development and application ideas for SiO[Formula: see text]-based anode materials.

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SiOx‐based anode material has emerged as one of the most promising candidates for graphite. However, poor electronic conductivity and relatively large volume effect hinder its practical application as anode lithium‐ion batteries (LIBs). Herein, a co‐modification approach using carbon and lithium borate hybrid coating simultaneously, is introduced to rationally exploit and improve the electronic and ionic conductivity of SiOx. When applied as anodes for LIBs, the SiOx@C@Li3BO3 sample exhibits superior cycling performance (81% capacity retention after 500 cycles at 1 A g−1). The enhanced electrochemical performance can be ascribed to the synergetic contribution of carbon and Li3BO3, which effectively accommodates the large volume change and improves the interfacial stability of SiOx@C@Li3BO3 during the lithiation/delithiation process. Herein, a versatile design strategy for alloy‐type anode materials is furnished.