Recently, aluminum-ion batteries have been receiving growing attention based on their low cost, good safety, and excellent capacity. In this work, the coral-like TeO 2 microwires synthesized by two-step thermal treatment can be revealed as excellent aluminum-ion battery cathodes. It delivers a capacity of 214.2 mAh g −1 and a relatively high-voltage plateau of ∼1.3 V at 200 mA g −1 and remains at 88.5 mAh g −1 over 100 cycles. Moreover, the reaction mechanism of TeO 2 is verified as the insertion of Al 3+ ions during discharging. More importantly, based on the design of acetylene black-modified separator, the higher reversible capacity of 152.0 mAh g −1 can be achieved over 150 cycles at 200 mA g −1 with a high Coulombic efficiency of 98.4%. At a higher current density of 500 mA g −1 , the battery can reach a stable capacity of 91.1 mAh g −1 over 700 cycles, displaying the superior long-term cycling stability, high capacity, and good rate capability. The results indicate that the coral-like TeO 2 microwires and acetylene black-modified separator can open up a new opportunity and be of great significance for further development of highcapacity and high-stability aluminum-ion batteries.