Hollow spheres structured materials have been intensively pursued due to their unique properties for energy storage. In this paper, hollow-in-hollow carbon spheres (HIHCS) with a multi-shelled structure were successfully synthesized using a facile hard-templating procedure. When evaluated as anode material for lithium-ion batteries, the resultant HIHCS anode exhibited superior capacity and cycling stability than HCS. It could deliver reversible capacities of 937, 481, 401, 304 and 236mAhg−1 at current densities of 0.1Ag−1, 1Ag−1, 2Ag−1, 5Ag−1 and 10Ag−1, respectively. And capacity fading is not apparent in 500 cycles at 5Ag−1. The excellent performance of the HIHCS anode is ascribed to its unique hollow-in-hollow structure and high specific surface area.