Thiswork investigated the effect of co-existing organic matters on aqueous Cr(VI) reduction by electrodeposited zero-valent iron (ED Fe0) at neutral pH. The ED Fe0 prepared in a solution containing mixture of saccharin, l-ascorbic acid and sodium dodecyl sulfate showed higher activity in reducing the aqueous Cr(VI) at neutral pH than that prepared without any organic presence. XRD and SEM indicated that the structure of ED Fe0 was significantly improved to nano-scale by the presence of organic mixture in the preparation solution. Further, the ED Fe0 activity in the Cr(VI) reduction at neutral pH was increased by the co-existence of citric acid or oxalic acid in the chromate solution. Electrochemical impedance spectroscopy (EIS) demonstrated that the corrosive current increased with the concentration of organic matter in the reaction solution. With the co-existing organic matters in the preparation solution, the ED Fe0 corroded more rapidly due to its nano-size, thus the Cr(VI) reduction by the ferrous iron was accelerated. With the co-existing organic matters in the reaction solution, the Cr(VI) reduction was accelerated by a Fe(II) complex as the main electron donor, and a prevention of the passivation due to the Fe(III) and Cr(III) complexes also accelerated the Cr(VI) reduction.