A composite anode consisting of hollow SnO2 microspheres covered by glass-like B2O3 layers was prepared via a combined hydrothermal-impregnation method, which results in much improved electrochemical performance in lithium ion batteries, relative to pristine SnO2 anodes. The cycling and rate capabilities of the SnO2–B2O3 composite anodes were investigated as a function of B2O3 content. The balance between increased electron-acceptor effect and compromised electronic conductivity due to addition of B2O3 is maximized around 20 wt% B2O3 loading. The best performing SnO2–B2O3 composite anode exhibits a specific capacity of 622.7 mAh g−1 up to 160 cycles, and is able to maintain a capacity above 528.6 mAh g−1 at rate of 5C. These enhanced performance characteristics are attributed to the unique composite structures consisting of the hollow SnO2 cores and the B2O3 buffer layers, which likely are beneficial for reducing the overall volume changes. Importantly, the decreased charge transfer resistance and increased Li+ diffusion coefficient, resulting from B2O3 coating, lead to overall improvement of rate performance for the composite anodes. Such-fabricated composite structures are stable during the Li+ insertion/extraction, thereby promoting cycling stability.