Nontransferrin‐bound iron is now recognized to exist by many workers. It is present in the serum of patients suffering from a wide range of disease states and may be induced by certain therapeutic treatments. The chemical nature of this iron pool is unknown but almost certainly it is a multicomponent pool including a considerable proportion of protein‐bound iron. Methods are required to separate and quantify these different components. The biological properties of the individual isoforms need to be established; it is possible that some forms are relatively nontoxic, while others are highly toxic. This paper reviews what is known about the nature of nontransferrin‐bound iron and describes the methods currently available to quantify this important serum component.