In this work, nanostructured macro-mesoporous hollow carbon spheres (MMHCSs) with high surface areas (396 m2 g−1) were synthesized as anode materials via a facile template-based method. A macroporous structure was created on the surfaces of the mesoporous hollow carbon spheres without destroying their spherical structure by etching in 20% HF. The unique nanostructure (imperfect hollow spheres) and the beneficial characteristics of amorphous carbon gave the MMHCSs a high reversible capacity of 530 mAh g−1 at 2.5 A g−1 over 1000 cycles. Remarkably, the MMHCSs retained an excellent rate capability of 180 mAh g−1 at 60 A g−1, which was superior to that of perfectly structured mesoporous hollow carbon spheres (without macropore (MHCSs)).