Aqueous flow batteries are considered very suitable for large-scale energy storage due to their high safety, long cycle life, and independent design of power and capacity. Especially, zinc-iron flow batteries have significant advantages such as low price, non-toxicity, and stability compared with other aqueous flow batteries. Significant technological progress has been made in zinc-iron flow batteries in recent years. Numerous energy storage power stations have been built worldwide using zinc-iron flow battery technology. This review first introduces the developing history. Then, we summarize the critical problems and the recent development of zinc-iron flow batteries from electrode materials and structures, membranes manufacture, electrolyte modification, and stack and system application. Finally, we forecast the development direction of the zinc-iron flow battery technology for large-scale energy storage.