A porous coral-structured Si/C composite as an anode material was fabricated by coating Si nanoparticles with a carbon layer from polyvinyl alcohol(PVA), erosion of hydrofluoric(HF) acid, and secondary coating with pitch. Three samples with different pitch contents of 30%, 40% and 50% were synthesized. The composition and morphology of the composites were characterized by X-ray diffractometry(XRD) and scanning electron microscopy(SEM), respectively, and the properties were tested by electrochemical measurements. The results indicated that the composites showed obviously enhanced electrochemical performance compared with that without secondary carbon coating. The second discharge capacity of the composite was 773 m A·h/g at a current density of 100 m A/g, and still retained 669 m A·h/g after 60 cycles with a small capacity fade of less than 0.23%/cycle, while the content of secondary carbon source of pitch was set at 40%. Therefore, the cycle stability of the composite could be excellently improved by regulating carbon content of secondary coating.