The successful use of the electrochemical process to produce compositional heterogeneous Co0.9Fe0.1(Cu) alloys is shown. Structure, composition, and morphology of the heterogeneous alloyed films, produced by the potentiostatic method, has been investigated by means of different techniques. Energy dispersive spectroscopy analyses reveal that the total amount of Co and Fe in the electrodeposits is strongly dependent on the Cu concentration in the plating solution at the potentiodynamic range investigated. The Co:Fe ratio does not change drastically due to Cu incorporation in the electrodeposits. It was also observed that by increasing the Cu content in the electrodeposits a granular morphology is obtained. Transmission electron microscopy was used to characterize the micromorphology and the heterogeneous composition of the alloys. The polycrystalline character of electrodeposits with a predominant face-centered cubic structure was characterized by using selected area electron diffraction and x-ray diffraction measurements.