AbstractThe development of advanced anode materials for lithium‐ion batteries that can provide high specific capacity and stable cycle performance is of paramount importance. This study presents a novel approach for synthesizing molecular‐level homogeneous carbon integration to porous SiO2 nanoparticles (SiO2@C NPs) tailored to enhance their electrochemical activities for lithium‐ion battery anode. By varying the ratio of the precursors for sol–gel reaction of (phenyltrimethoxysilane (PTMS) and tetraethoxysilane (TEOS)), the carbon content and porosity within SiO2@C NPs is precisely controlled. With a 4:6 PTMS and TEOS ratio, the SiO2@C NPs exhibit a highly mesoporous structure with thin carbon and the partially reduced SiOx phases, which balances ion and charge transfer for electrochemical activation of SiO2@C NPs resulting remarkable capacity and cycle performance. This study offers a novel strategy for preparing affordable high capacity SiO2‐based advanced anode materials with enhanced electrochemical performances.image