Na0.282V2O5 nanorods have been successfully prepared using a facile hydrothermal reaction followed by a calcination treatment, which is then used as a cathode for lithium batteries and sodium batteries for the first time. The crystal structure is refined to be a monoclinic lattice, which contains 3D tunnels along the b-axis. The Na ions are located inside the tunnels and form “pillar effect” to prevent the collapse of the crystal structure. As cathode material for lithium batteries, the Na0.282V2O5 nanorods deliver a high discharge specific capacity of 264, 186, 191 and 149 mA h g−1 at the current density of 50, 500, 1000 and 1500 mA g−1, respectively. The Na0.282V2O5 nanorods demonstrate the excellent cycling performance up to 400 cycles at 1 and 1.5 A g−1. Importantly, as cathode material for sodium batteries, Na0.282V2O5 exhibits superior long-term cyclic stability up to 1000 cycles at 0.3 A g−1. The results of ex-situ XRD, EIS and first-principle calculation indicate that the Na0.282V2O5 possesses good electrical conductivity and structural stability. Our work demonstrates that the Na0.282V2O5 material could be considered as a potential cathode for lithium-ion batteries, and even sodium ion batteries.