Vanadium oxides as cathode for zinc-ion batteries have attracted much attention because of their high theoretical capacity, flexible layered structure and abundant resources. However, cathodes are susceptible to the collapse of their layered structure and the dissolution of vanadium after repeated long cycles, which worsen their capacities and cycling stabilities. Herein, a synergistic engineering of calcium-ion intercalation and polyaniline coating was developed to achieve the superior electrochemical performance of vanadium pentoxide for zinc-ion batteries. The pre-intercalation of calcium-ion between vanadium pentoxide layers as pillars increase the crystal structure’s stability, while the polyaniline coating on the cathodes improves the conductivity and inhibits the dissolution of vanadium. This synergistic engineering enables that the battery system based-on the polyaniline coated calcium vanadate cathode to deliver a high capacity of 406.4 mAh·g⁻¹ at 1 A·g⁻¹, an ultralong cycle life over 6000 cycles at 10 A·g⁻¹ with 93% capacity retention and high-rate capability. The vanadium oxide cathode with synergistic engineering of calcium-ion intercalation and polyaniline coating was verified to effectively improve the electrochemical performance of zinc-ion batteries.