In this work, we report on the first synthesis of novel ultrathin (α-Fe2O3)1−x (V2O5) x solid-solution nanoplates via a facile one-pot hydrothermal method. Shape selection and crystallographic orientation show closely interrelated with the V2O5-modification. Irregular α-Fe2O3 particles with random exposed facets were obtained in the absence of vanadium sources. When tested as anode materials for lithium batteries, the ultrathin (α-Fe2O3)1−x (V2O5) x nanoplates show greatly enhanced performance of Li storage. Under the condition of high current density of 1C, the ultrathin (α-Fe2O3)1−x (V2O5) x nanoplates were capable of retaining a specific capacity of 771mAhg−1 over 100 cycles. Even when cycled at 5C and 10C, comparable capacities of 482 and 365mAhg−1 could be achieved, indicating an excellent rate capability.