To explain the abnormal stoichiometry found in Fe I I I /bis(2-hydroxyethyl)dithiocarbamate potentiometric titrations, i.e. 2:1 instead of 3:1 conductometric studies, determination of the conditional standard potential for the bis(2-hydroxyethyl)dithiocarbamate oxidation, stability constants and decomposition kinetics studies have been made. A mechanism is proposed to elucidate the phenomenon.