A facile and efficient electrostatic-assembly method to fabricate ball-milling-silicon@carbon/reduced-graphene-oxide composite (bmSi@C/rGO) has been developed. In the fabrication process, chitosan (CTS), as a charged bridge, connected ball milling silicon (bmSi) and graphene oxide (GO), and then was transformed into carbon coating by heat treatment. The carbon coated ball milling silicon (bmSi@C) particles were distributed evenly between the sheets of reduced graphene oxide (rGO). Therefore, the carbon coating and the wrinkled graphene sheets formed a superior conductive matrix and a buffer zone. The composite used as anode material exhibited high reversible capacity of 935.77mAhg−1 and 71.9% capacity retention after 100 cycles. The excellent electrochemical properties are attributed to the well-designed structure, in which both the carbon layer and the rGO play an important role for improving the whole electrical conductivity and preventing the silicon from pulverization.