Mesoporous Sn/SnO2/carbon composites with uniformly Sn/SnO2 embedded within the carbon pore walls have been rationally designed and synthesized. These nanocomposites have been characterized by XRD, SEM, TEM, XPS and tested as negative electrodes in a cell using lithium foil as the counter electrode. The inclusion of metallic Sn in SnO2/CMK-3 resulted in a unique, ordered structure and provided a synergistic effect which resulted in an impressive initial reversible capacity of 799mAhg−1. In addition, at a higher current of 800mAg−1, the heterostructure was able to provide a stable capacity of 350mAhg−1. Furthermore, a retention capacity of ∼670mAhg−1 was obtained after 60 cycles.