A robust voltammetric method has been developed and validated for the determination of Fe(Ⅱ) and Fe(Ⅲ) in pharmaceutical iron polysaccharidic complexes. Undesirable low molecular weight iron complexes, at concentration about 3% in the pharmaceutical formulation, can be easily determined with good accuracy and precision. This methodology can be proposed as a viable, environmentally sustainable substitute for the conventional Normal Pulse Polarographic method in US Pharmacopeia, with better analytical figures of merit, and reduced Hg consumption. A deeper insight in Fe(Ⅱ) and Fe(Ⅲ) composition can be gained by the combined use of a new potentiometric technique after chemical decomposition of the complex. A robust voltammetric method has been developed and validated for the determination of Fe (II) and Fe (III) in pharmaceutical iron polysaccharidic complexes. Undesirable low molecular weight iron complexes, at concentration about 3% in the pharmaceutical formulation, can be readily determined with This accuracy measure can be proposed as a viable, affordable sustainable method for the conventional normal Polarographic method in US Pharmacopeia, with better analytical figures of merit, and reduced Hg consumption. A deeper insight in Fe (II) and Fe (Ⅲ) composition can be gained by the combined use of a new potentiometric technique after chemical decomposition of the complex.