Three-dimensionally ordered macro-porous Sn-C composites were prepared by using polystyrene microsphere as a template. The Sn-C composites were composed of well-interconnected pore with circular shape and wall structure with wall thickness of a few tens of nano-meters. This porous three-dimensional structure is readily and uniformly accessible to the electrolyte, which facilitates lithium ion diffusion during charge-discharge reactions. The wall thickness of the composites was increased as the increase of Sn content of the composite. From EDS analysis, it is confirmed that the Sn was dispersed uniformly in Sn-C composites. The capacity was increased as the Sn content increased, which is due to Sn anode with high capacity. The Sn-C composites with high Sn content showed superior cyclic performances. Such enhancement is ascribed to the thick wall thickness and small pore size of the sample with high Sn content. The Sn-C composite with Sn 30 wt% showed relatively high capacity and stable cycle life, however, the stability of the 3-dimensional structure should be enhanced by further work.