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Sustainable, renewable and environmental friendly anode materials are key factors to energy storage devices. We report a novel metal-doping strategy to enhance electrochemical performance of silicon/carbon nanocomposite (Co-Si/C) anode via pyrolysis of cobalt-coordinated poly(dimethylsilyene)diacetylenes. The Co-Si/C nanocomposite anodes exhibited promising superior cyclic properties and kept a high discharge capacity of about 1105 mAh g-1. They maintained a specific capacity of 905 mAh g-1 after 100 cycles at 100 mA g-1 with an average coulombic efficiency of 81.9 % and a high specific capacity of 540 mAh g-1 after 1000 cycles at 500 mA g-1 with an average coulombic efficiency of 99 %. The Co-Si/C anode composite preserved the structural integrity after the electrochemical tests, demonstrating the potential of efficient and stable electrochemical performance.