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 935.77 mAh g(-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. (C) 2016 Elsevier Ltd. All rights reserved.