Three-dimensional (3D) a-Fe2O3@graphene aerogel (a-Fe2O3@GA) composites with an a-Fe2O3 content as high as 54wt% were prepared via a gas-liquid interfacial assembly method. It was found that the a-Fe2O3 nanoparticles were well dispersed and embedded into the 3D porous structure of graphene aerogel (GA). Compared with that (SBET =82m2 g−1) of pristine a-Fe2O3, the resulting composites exhibited much higher specific surface area (SBET =261m2 g−1). The composites used as anode materials for lithium ion batteries maintained a high reversible capacity of 745mAhg−1 at a current density of 100mAg−1 or more than 240mAhg−1 at a current density of 2000mAg−1 after 100 cycles, and exhibited superior stable electrochemical cycling performance and excellent rate capability. The superior electrochemical performances were attributed to the synergistic effects of the unique 3D porous structure of the composites with high contents of well dispersed a-Fe2O3.