The energy storage properties of layered metal vanadate, especially alkali metal vanadates have been extensively studied. Metal vanadates have a more robust electrochemical output in contrast with pristine vanadium oxides. However, the detailed processes underlying the efficiency contrast of vanadates and vanadium oxides have rarely been studied. Herein a facile hydrothermal and low-temperature polymerization method was introduced to synthesize KV3O8 and KV3O8@PPy nanowire bundles as anode material for an aqueous rechargeable Lithium batteries. The nanowires are composed of KV3O8·0.59H2O calculated using thermal gravimetric analysis (TGA). Successfully synthesized layered vanadium based KV3O8 0.59H2O (KVO) and KV3O8 0.59H2O@PPy (KVO@PPy) nanowires and investigated the source of the improved electrochemical efficiency of PPy coated potassium vanadates compared to pristine KVO using crystal structure analysis and electrochemical tests. We demonstrated increase in electrochemical stability for KVO@PPy caused by synergistic effect of K+ in vanadate nanowires and PPy coating. In KVO the oxygen atoms have close contact with the K ions, and the stable K+ serve as ‘‘pillars” between interlayers to shield the layered structures from collapse during the charge/discharge phase, while the PPy reduces charge transfer resistance. This research adds helps us design better electrode materials to be used as an anode material for ARLB using alkali metal vanadate.