Anaerobic digestion is widely used in the treatment of industrial wastewater,excess activated sludge,municipal waste,crop straw and livestock manure,with the functions of environmental protection and energy recovery. This review summarizes and evaluates the present knowledge of effects of different states of Fe( ZVI,Fe( II),Fe( III)) on hydrogen and methane production in anaerobic digestion process. The potential promotion effects of iron oxides nanoparticles( IONPs),especially magnetite nanoparticles on anaerobic digestion are also mentioned. Fe plays important role in transporting electron,stimulating bacterial growth and increasing hydrogen and methane production rate by promoting enzyme activity. Adding Fe with different morphologies and valence states in anaerobic digestion to increase biogas( hydrogen and methane) production and enhance organic matter degradation simultaneously,which has attracted many scientists’ attention in recent years. Rapid progress in this area has been made over the last few years,since Fe is essential to the fermentative hydrogen and methane production,while few is known about how Fe affects the fermentative biogas production. This review is significant to maintain the stable operation of the biogas project. Anaerobic digestion is widely used in the treatment of industrial wastewater, excess activated sludge, municipal waste, crop straw and livestock manure, with the functions of environmental protection and energy recovery. This review summarizes and evaluates the present knowledge of effects of different states of Fe (ZVI, Fe (II), Fe (III)) on hydrogen and methane production in anaerobic digestion process. The potential promotion effects of iron oxides nanoparticles (IONPs), especially magnetite nanoparticles on anaerobic digestion are also mentioned. transporting electron, stimulating bacterial growth and increasing hydrogen and methane production rate by promoting enzyme activity. increasing Fe and different morphologies and valence states in anaerobic digestion to increase biogas (hydrogen and methane) production and enhance organic matter degradation simultaneously, which has attracted many scientists ’attention in recent years. Rapid progress in this area has been ma de over the last few years, since Fe is essential to the fermentative hydrogen and methane production, while few is known about how Fe affects the fermentative biogas production. This review is significant to maintain the stable operation of the biogas project.