We have used the recently established linear correlation between the total intensities of theL3,2‘‘white lines’’ in electron energy‐loss spectroscopy and the number of unoccupied 3dstates to probe the local electronic structure in epitaxially grown Co–Cr thin films. The significant enhancement of saturation magnetization measured for these epitaxial films, when compared to homogenized bulk alloys, has been correlated directly to the unoccupied 3dstates to the Co atoms in these materials. These measurements are the first direct electronic structure evidence that may support models associating the enhancement of saturation magnetization withintragranularsegregation in Co–Cr thin films. ©1995 American Institute of Physics.