The effects of peanut mixed cropping with five different gramineous plants on apoplast iron accumulation and reducing capacity of peanut were investigated by soil culture experiment. The results showed that mixed cropping of maize, barley, oats, wheat, and sorghum with peanut could improve iron nutrition of peanut respectively. The phytosiderophores excretion rate of barley, oats and wheat were much higher than that of maize, and the phytosiderophores excretion rate of sorghum was lower than that of maize. In comparison with peanut in monocropping the iron content in different organs of peanut mixed with maize, barley, oats, wheat and sorghum were increased. The Fe content in root apoplast of peanut mixed with five different gramineous was gradually increased and higher than that of peanut in monocropping at different growth days. At the same time, the mixed cropping systems remarkably improved the soil Fe availability in the rhizosphere and root Fe reducing capacity of peanut. The higher root Fe (III) reducing capacity and much more available Fe in the rhizospe (III) of peanut in mixed cropping played an important role in improving iron nutrition of peanut.