Owing to scientific importance associated with highly reactive surfaces, the research concerning inorganic single crystals with a large percentage of exposed high-index facets has attracted much attention. In current research, α-Fe2O3 nanocubes exposed with (012) active facet was firstly synthesized via a hydrothermal method. And then a freeze-drying approach was utilized to construct nanostructured Fe2O3/graphene composite. The as-obtained composite exhibited s higher BET surface area than that of bare α-Fe2O3 nanocubes. When evaluated for lithium storage properties, the Fe2O3/graphene rendered remarkable electrochemical cycle stability and high rate performance. At the rate of 300 mA g−1, a high reversible discharge capacity of 1136 mAh g−1 was obtained up to 200 cycles. In addition, the excellent rate performance was also achieved. Excellent electrochemical properties are probably ascribed to the synergistic effect of α-Fe2O3 nanocubes and graphene sheets, as a result of smart structure design via a freeze-drying route. This strategy with merits of rational construction and scalable production could establish new perspective for diverse composites towards commercial application.