This paper reports a study of grain boundary and free surface segregation in iron alloys. Scanning Auger electron spectroscopy has been used to analyze the extent and spatial distribution of the segregants. It is found that there is a similarity between free surface and grain boundary segregation for vacuum‐melted (vm) and zone‐refined (zr) materials. S and O are the primary segregants to grain boundaries for vm samples, while N is the predominant segregant for zr material. When O and S are the primary segregated elements, a site competition between them is observed on both the free surface and at grain boundaries. On the free surface the site competition is dependent on grain orientation.