A microporous Si-O-C composite material was prepared by pyrolysis of a blend of polysilane, (Ph2Si)(0.85)(PhSi)(0.15) (1) and polystyrene (1:1 in weight) at 1000 degrees C. This material electrochemically performed well, offering a capacity of more than 600 mA h g(-1) and a good cycle life. Our Li-7 NMR analysis confirmed the possibility of several electrochemical active sites for lithium storage in this new composite material.