Coordinated electrochemical effect between Li3VO4 and NiO occurs in Li3VO4/NiO/Ni electrodes owing to the close potential regions of lithiation and delithiation for Li3VO4 and NiO. Remarkably, Li3VO4/NiO/Ni with bottom nanowalls and upper micro-flowers architecture undergoes a novel coordinated electrochemical reconstruction owing to well coordinated morphology variation of Li3VO4 and NiO in lithiation and delithiation process, which leads to the formation of a new symmetrical porous architecture in cycling, resulting in superior electrochemical performance. At a specific current of 70 mA g−1, it exhibits discharge and charge capacity of 860 and 631 mAh g−1 in the initial cycle, maintaining of 612 and 604 mAh g−1 after 100 cycles. After 60 cycles at various specific currents from 54 to 2700 mA g−1, the discharge and charge capacity can restore to 612 mAh g−1 when reverting the specific current to 54 mA g−1.