SThe interaction of Fe(III) with niacin and pyridoxine was investigated by UV-Vis.spectrophotometry. The metal to ligand ratio for Fe(III)-niacin system was found to be approximately 1 : 3 and for Fe(III)-pyridoxine system it was 1 : 1. The redox properties of uncoordinated Fe(III)/Fe(II) system is reversible at platinum electrode and in presence of the ligands the system was found to be quasi-reversible in nature. It was also found that in every case the system was diffusion controlled.