The orthorhombic and hydrated vanadium pentoxide (V2O5) films are fabricated via a facile electrodeposition method followed with a controllable annealing process. Served as sodium ion batteries (SIBs) cathode, the hydrated V2O5 film exhibits enhanced sodium storage performance over the orthorhombic V2O5 film, originating from faster diffusion reaction kinetics, better electrochemical reaction reversibility, and smaller electrochemical reaction resistance. To be specific, the hydrated V2O5 film maintains a high capacity of 166mAhg−1 after 100 charge-discharge cycles at 200mAg−1 between −1.5V and 0.5V (vs. an Ag/Ag+ reference electrode). Moreover, it reveals outstanding rate capability with reversible discharge capacities of 133mAhg−1 at 1000mAg−1 and 121mAhg−1 at 2000mAg−1, which are higher than those of orthorhombic V2O5 film (41mAhg−1 at 1000mAg−1 and 34mAhg−1 at 2000mAg−1). The significant enhancement in sodium-ion storage capacity and high-rate performance of the hydrated V2O5 film is mainly due to its lager interlamellar spacing, which can promote the insertion/extraction of Na+, and the presence of V4+ accompanied with oxygen vacancies, which might improve the electronic conductivity and alleviate the stress caused by volume expansion.