Vanadium diselenide (VSe2) is a transition metal dichalcogenide with metallic conductivity, which makes it a potentially promising electrode material for electrochemical applications. However, the development of VSe2 electrodes for such applications has been severely hampered by the difficulty of preparing nanosized products. In this work, a new facile solvothermal synthesis process is developed and optimized to synthesize ultrathin VSe2 nanosheet assemblies. To obtain the ultrathin nanosheets, N-methyl pyrrolidone, which has similar surface energy to many transition metal dichalcogenides, was used as the solvent to limit the crystal growth along the c-axis direction. The resulting ultrathin VSe2 nanosheets exhibit good performance toward alkaline ion (Li+ and Na+) storage, which can be significantly enhanced by carbon coating. Specifically, the carbon-coated VSe2 nanosheets can deliver high capacities of 768 mA h g-1 (Li+ storage) and 571 mA h g-1 (Na+ storage) along with outstanding stability.