A simple and inexpensive route is developed to synthesis the Sb thin film sandwiched between the reduced graphene oxide and the Ni foam (RGO-SbTF-Ni) by a galvanic replacement reaction along with a pulse electrophoretic deposition route. As a binder-free anode material for lithium ion batteries, the RGO-SbTF-Ni exhibits a high initial discharge capacity of 872.9mAhg−1 and an enhanced coulombic efficiency of 66.0% at a current density of 100mAg−1 in the first cycle. In addition, a substantial discharge capacity of 424.1mAhg−1 can be retained even after 50 repeated cycles. The enhanced performances of the designed binder-free anode material can be attributed to the novel hierarchical sandwich laminated structure with an excellent electrical contact, and the synergistic effect between the Sb thin film with high specific capacity and flexible RGO with good buffer effect to alleviate the strain caused by the large volume change.