The interaction of pyridoxal isonicotinoyl hydrazone (PIH) and salicylaldehyde isonicotinoyl hydrazone (SIH), two important biologically active chelators, with iron has been investigated by spectrophotometric methods. High iron(III) affinity constants were determined for PIH, logβ2=37.0 and SIH, logβ2=37.6. The associated redox potentials of the iron complexes were determined using cyclic voltammetry at pH7.4 as +130mV (vs normal hydrogen electrode, NHE) for PIH and +136mV(vs NHE) for SIH. These redox potentials are much higher than those corresponding to iron chelators in clinical use, namely deferiprone, -620mV; desferasirox, -600mV and desferrioxamine, -468mV. Although the positive redox potentials of SIH and PIH are similar to that of EDTA, namely +120mV, the iron complexes of these two hydrazone chelators, unlike the iron complex of EDTA, do not redox cycle in the presence of vitamin C. These properties render PIH and SIH as excellent scavengers of iron, under biological conditions. Both SIH and PIH scavenge mononuclear iron(II) and iron(III) rapidly. These fast kinetic properties of the hydrazone-based chelators provide a ready explanation for the adoption of SIH in fluorescence-based methods for the quantification of cytosolic iron(II).