A highly precise and rapid method for the quantitative estimation of iron traces by substoichiometric isotope dilution analysis has been described. The method involves the extraction of spiked (Fe-59) iron(III) with substoichiometric amounts of acetylacetone into chloroform at pH 2.0. The proposed method is free from interferences of various closely related foreign ions, thereby establishing the selectivity of the proposed technique. The present method has also been applied to different certified alloys without any pre-separation and the trace quantities of iron are successfully evaluated.