Iron fluoride cathode for lithium batteries intrigues researchers for decades due to high capacity and low cost, but suffers from poor electronic and ionic conductivity. Hierarchical micro/nano construction with preferred orientation growth can shorten ion diffusion pathway and facilitate electron transportation without inducing side reactions. Here, FeF3·0.33H2O hierarchical microspheres self-assembled by octagonal single crystal slices are prepared. Benefiting from the artful structure, SAED and XRD characterizations confirm that the octagonal single crystal slices provides more lithium ions intercalation positions (4c sites). Electrochemical tests demonstrate that the well designed FeF3·0.33H2O single crystal (FFH-S) delivers 30 mAh g−1 higher capacity (172 mAh g−1 at 0.1C) than the common FeF3·0.33H2O polycrystal (FFH-P). In-situ XRD combined with theoretic calculation elucidate the difference in lithium storage capacity. Instructive argument that single crystal octagon slices with [110] oriented growth provide more active sites for lithium ions intercalation contributes to the preparation of high performance iron fluoride cathode materials for rechargeable battery.