A self‐templated strategy is developed to fabricate hierarchical TiO2/SnO2 hollow spheres coated with graphitized carbon (HTSO/GC‐HSs) by combined sol–gel processes with hydrothermal treatment and calcination. The as‐prepared mesoporous HTSO/GC‐HSs present an approximate yolk‐double–shell structure, with high specific area and small nanocrystals of TiO2 and SnO2, and thus exhibit superior electrochemical reactivity and stability when used as anode materials for Li‐ion batteries. A high reversible specific capacity of about 310 mAh g−1 at a high current density of 5 A g−1 can be achieved over 500 cycles indicating very good cycle stability and rate performance.