A process was proposed to prepare Sn/C microsphere composite anode for Li-ion batteries. The Sn/C microsphere composite was successfully prepared by adding SnO2 powder to the water phase during the inverse emulsion curing of phenolic resin, followed by carbonization and carbothermal reduction of Sn in Ar atmosphere at 900 degrees C. Scanning electron microscopy and X-ray diffractometry analysis showed that the SnO2 powders were encased within the carbon microspheres, and were carbothermally reduced to crystalline Sn by the carbonized phenolic resin. Being encased in carbon microsphere, Sn presented the improved cyclability. This process paves an effective way to prepare high performance anode materials for Li-ion batteries. (c) 2006 The Electrochemical Society.