Dual-ion batteries (DIBs) are a new kind of energy storage device that store energy involving the intercalation of both anions and cations on the cathode and anode simultaneously. They feature high output voltage, low cost, and good safety. Graphite was usually used as the cathode electrode because it could accommodate the intercalation of anions (i.e., PF6−, BF4−, ClO4−) at high cut-off voltages (up to 5.2 V vs. Li+/Li). The alloying-type anode of Si can react with cations and boost an extreme theoretic storage capacity of 4200 mAh g−1. Therefore, it is an efficient method to improve the energy density of DIBs by combining graphite cathodes with high-capacity silicon anodes. However, the huge volume expansion and poor electrical conductivity of Si hinders its practical application. Up to now, there have been only a few reports about exploring Si as an anode in DIBs. Herein, we prepared a strongly coupled silicon and graphene composite (Si@G) anode through in-situ electrostatic self-assembly and a post-annealing reduction process and investigated it as an anode in full DIBs together with home-made expanded graphite (EG) as a fast kinetic cathode. Half-cell tests showed that the as-prepared Si@G anode could retain a maximum specific capacity of 1182.4 mAh g−1after 100 cycles, whereas the bare Si anode only maintained 435.8 mAh g−1. Moreover, the full Si@G//EG DIBs achieved a high energy density of 367.84 Wh kg−1at a power density of 855.43 W kg−1. The impressed electrochemical performances could be ascribed to the controlled volume expansion and improved conductivity as well as matched kinetics between the anode and cathode. Thus, this work offers a promising exploration for high energy DIBs.