SnO2@C nanocomposites are easily synthesized in a large scale by the hydrolysis of Sn4+ ions in a polyacrylic acid (PAA) hydrogel system, followed by the decomposition of Sn(OH)4 and carbonization of PAA by heat treatment in one-system. The SnO2@C nanocomposites contain uniform ultrafine SnO2 nanoparticles (≈4.3 nm) homogenously embedded in a three-dimensional carbon matrix. This unique structure efficiently suppresses the particle pulverization and aggregation of SnO2, thus maintaining the electrode integrity during long-term lithiation/delithiation process. The discharge capacity of SnO2@C nanocomposites is maintained at ∼597.3 mAh g−1 after 220 cycles. This scalable approach has great potential in the applications of high-capacity anodes in Li-ion batteries.