Flower-like Fe3O4/graphene aerogel (Fe3O4/GA) composite was prepared by water-bath vitamin C reduction self-assembly process followed by a heat treatment under N2 atmosphere. The morphological and structural results demonstrate that 3D flower-like Fe3O4 particles are homogenously embedded into the 3D conductive network of graphene nanosheet aerogels. Based on this unique structure, flower-like Fe3O4/GA composite exhibits a high reversible capacity of 797 mAh g−1 at 0.2 A g−1, and good rate capacity of 551 mAh g−1 at 3.2 A g−1 as well as excellent cycling performance with a stable capacity of ~1138 mAh g−1 after 100 cycles at 0.2 A g−1 compared with bare flower-like Fe3O4 electrode. Our work demonstrates this self-assembly approach can be used to prepare other electroactive metal oxides/graphene composite for the application of lithium ion batteries.