Vanadium oxides have recently attracted widespread attention due to their unique advantages and have demonstrated promising chemical and physical properties for energy storage. This work develops a mild and efficient method to stereoassemble hollow V2O5@FeOOH heterostructured nanoflowers with thin nanosheets. These dual-phased architectures possess multiple lithiation voltage plateau and well-defined heterointerfaces facilitating efficient charge transfer, mass diffusion, and self-reconstruction with volumetric strain. As a proof of concept, the resulting V2O5@FeOOH hollow nanoflowers as an anode material for lithium-ion batteries (LIBs) realize high-specific capacities, long lifespans, and superior rate capabilities, e.g., maintaining a specific capacity as high as 985 mAh g-1 at 200 mA g-1 with good cyclability.