In this work, a novel composite consisting of nanosized silicon highly dispersed within the porous, elastic and conductive oxide/carbon matrix has been developed as an anode candidate for lithium ion batteries. The composite was prepared by a mechanochemical reaction between SiO and Li under ball milling followed by a carbon coating using the pyrolysis of poly(vinyl chloride)–co-vinyl acetate. The porous structure can effectively suppress the volume change of silicon during the electrochemically Li-alloying process. No obvious capacity fading was observed up to 100 cycles with a stable capacity of 620mAhg−1. The factors influencing the microstructure and the electrochemical behavior of the composite were discussed.