As an emerging battery technology, metal-air flow batteries inherit the advantageous features of the unique structural design of conventional redox flow batteries and the high energy density of metal-air batteries, thus showing great potential as efficient electrochemical systems for large-scale electrical energy storage. This review summarizes the operating principles and recent progress of metal-air flow batteries from a materials and chemistry perspective, with particular emphasis on the latest advanced materials design and cell configuration engineering, which the authors divide into three categories based on the anode