3D flower-like Al-doped V6O13 and Al/Na co-doped V6O13 have been fabricated via a facile hydrothermal method using C2H2O4·2H2O, V2O5, Al(NO3)3·9H2O, and NaNO3 as raw materials. The microstructure of the samples was characterized by XRD, EDS, XPS, FESEM, and TEM. The results indicated that Al and Na ions co-doping improved the electrochemical performance of V6O13, including the specific discharge capacity and cycling stability. When the doped mole ratio of Al to V and Na to V were 0.033 and 0.020, respectively, the sample exhibited the best electrochemical performance with initial discharge specific capacity of 514 mAh/g. After 80 cycles, the capacity retention was 70.3%. The enhanced electrochemical performance originates from its superior structural reversibility, enhanced lithium diffusion coefficient and improved electrical conductivity.