Abstract Rationally designing the morphology of V2O5 nanomaterial has caused great significance in the applications of lithium ion storage due to its promising physico-chemical properties. Herein, various V2O5 hierarchical structures have been first successfully synthesized via a facile hydrothermal method followed by an annealing treatment. The V2O5 morphologies undergo a nanoribbon → nanosheet →micro flower structure process with hydrothermal reaction increasing time. After surfactant-assisted hydrothermal process, four types of as-prepared surfactants modified V2O5 exhibit extraordinary valuable morphologies and excellent electrochemical properties in comparison with unmodified V2O5. Especially, cetyltrimethyl ammonium bromide modified V2O5 (defined as V5@CTAB) displays a unique morphology of the combination of three-dimensional (3D) turbine-like micro flowers and low-dimensional nanoparticles. As a thin film cathode material free of binders and conductive agent for lithium-ion batteries, V5@CTAB shows the exceptional high reversible specific capacity of 237 mAh g−1 at current density of 200 uA cm−2, outstanding rate performance, as well as an excellent cycling stability (only 0.10% capacity loss per cycle for 35 cycles). The excellent electrochemical performance might be ascribed that the unique 3D turbine-like microstructure favors the efficient contact between active material and electrolyte, providing more efficient 3D electron transfer pathways, shortening Li+ diffusion distances and thus leading to fast kinetics. These advantages make the 3D turbine-like V2O5 micro flowers structure a promising candidate of the cathode material for lithium-ion batteries.