Changes taking place in the fine structure of the cobaltKedge in Ni‐Co solid solutions indicate a decline in the 3d‐4shole density at cobalt atom sites. Changes in the NiKedge in the same alloys suggest that the hole density at nickel atoms increases, thus supporting the rigid‐band model for these alloys.Significant changes in the NiKedges of fcc (gamma) Ni‐Fe solid solutions suggest that the rigid‐band model may be valid for these alloys also. It does not appear to be applicable, however, to bcc (alpha) solid solutions. In both alloy types, the fine structure at the FeKedge remained unchanged. Good agreement was obtained with magnetic measurements on bcc Ni‐Fe alloys.