Abstract CeO2 is known to have considerable potential for use as a novel anode material in lithium-ion batteries, but it has inherently low electronic conductivity and low capacity retention due to volumetric or morphological changes during charge–discharge cycling. In this study, we developed an effective synthetic strategy based on the modified Stober method for the first time to obtain CeO2–carbon composite spheres (CeO2–CCS) using PAA (poly(acrylic acid)) and compared it with CeO2–carbon core shell (CeO2@C) formed without PAA. The CeO2–CCS showed that the CeO2 nanoparticles are well dispersed in the composite spheres with a rough surface, and the surface is coated with an amorphous carbon layer with a thickness of approximately 1–2 nm. This novel architecture provides good access to the electrolyte and accommodates the volume expansion of CeO2 during electrochemical cycling, thereby showing the rate capability and cyclability of CeO2–CCS higher than CeO2@C. We also identified the reaction mechanism of CeO2 using synchrotron-based X-ray absorption spectroscopy. This study provides a comprehensive understanding and strategy for CeO2 as a promising material for anode materials in lithium-ion batteries.