A high-performance carbon–Si composite anode for lithium rechargeable batteries was developed. Si powder was coated with amorphous carbon by pyrolyzing polyvinyl chloride and chlorinated polyethylene at 900°C for 2h. The electrochemical performance of the carbon–Si composite anode depended on the Si particle size and the carbon content of the composite. A carbon–nano-size Si (average size 50nm) composite with 48wt.% carbon showed an excellent performance. The coulombic efficiency in the first cycle was 69.2% and the second cycle reversible discharge capacity of 970mAhg−1. The capacity fade on cycling was 0.24% per cycle during the first 40 cycles. The carbon–micron-sized Si (average size 4μm) composite showed a high coulombic efficiency of 78.6% in first cycle, but with poor cycling performance. The capacity fade within 30 cycles was 1.7% per cycle. The effect of the chlorine content in the precursor on the cycling performance was not detectable.