In recent years, with the growing demands for large-scale applications of rechargeable batteries, the eco-friendly sodium-ion batteries with low price and high charge–discharge rates have attracted much attention. In this work, using a simple hydrothermal process, we successfully synthesize single crystalline VO2 parallel ultrathin nanosheets for the cathode material in sodium-ion batteries. Combined the XRD, XPS, electrochemical measurements with the first-principles simulations, the charge–discharge performance and the mechanism of Na insertion and extraction into/from the VO2 structure have systematically studied. The results reveal that the Na x VO2 products possess semiconductor properties and the interlayer distance almost keeps constant during charge and discharge process, which is beneficial to the transmission of Na ions. The charge and discharge process occurs between Na0.3VO2 and NaVO2. Even at a large current density of 500 mA g−1, the discharge capacity can still keep at 108 mAh g−1. As a cathode material for sodium-ion batteries, the results are outstanding and provide a possibility of large-scale applications for rechargeable sodium-ion batteries.