Silicon/carbon composite anode materials were prepared by pyrolyzing the phenol-formaldehyde resin (PFR) mixed with silicon and graphite powders. Scanning electron microscopic (SEM) observation showed that the morphology stability of the composite electrodes can be retained during cycling. A structure evolution mechanism is proposed to illuminate the enhancement of cycleability of the composite electrode. The composite used as anode material for lithium ion batteries possesses a reversible capacity of over 700mAh/g.