Aluminum-air cells have attracted a lot of interests because they have the highest volumetric capacity density in theory among the different metal-air systems. To overcome the self-discharge issue of aluminum, a microfluidic aluminum-air cell working with KOH methanol-based anolyte was developed in this work. A specific capacity up to 2507 mAh g−1 (that is, 84.1% of the theoretical value) was achieved experimentally. The KOH concentration and water content in the methanol-based anolyte were found to have direct influence on the cell performance. A possible mechanism of the aluminum reactions in KOH methanol-based electrolyte was proposed to explain the observed phenomenon.