The electrochemical behaviors of pyrolized polyacrylonitrile (PAN) were investigated to be applied as a carbon source in a metal-carbon composite anode in Li-ion batteries. Pyrolized PAN showed a porous structure with a reversible capacity approximately 300 mA h g(-1). A pyrolyzed PAN based Sn/C composites were synthesized from SnO and PAN using a high energy ball milling followed by carbothermal reduction, and the Sn particles with diameters of 100-200 nm were randomly embedded on the carbon matrix. The composite electrode exhibited a relatively large capacity and an excellent cycle behavior. The enhanced electrochemical performances of this composite were attributed to the role as a matrix and porous nature of pyrolyzed PAN which accommodated a large volume expansion of the Sn during the reaction with Li, the increased electrical conductivity of pyrolyzed PAN and the uniformly dispersed nanometer sized Sn that formed during the cycling. (C) 2012 Elsevier B.V. All rights reserved.