Orthorhombic single crystal V2O5 sheets with lateral dimensions of 4–6μm were synthesized by a facile one-pot organics-assisted pyrolysis method. TG-MS measurements revealed the intrinsic reaction mechanism of the as-prepared V2O5 sheets. As cathode materials for the lithium ion batteries (LIBs), V2O5 sheets delivered high initial discharge capacity of 310mAhg−1 and the coulombic efficiency remained close to 100% during the 50 charge-discharge cycles. Good electrochemical performance is attributed to the unique sheet structure, which increases the contact area between the active material and the electrolyte. Moreover, the structure greatly facilitates intercalation and deintercalation of Li+ ions and electron transport. Developed approach is simple, low cost and has excellent scalability for preparing V2O5 sheets as high-performance LIBs cathodes.