Nickel-copper foam electrodes with pore gradient micro framework and nano-ramified wall have been prepared by using an electrochemical deposition process. Growth habit of nickel-copper co-deposits was quite different from that of pure nickel deposit. In particular, the ramified structure of the individual particles was getting clear with chloride ion content in the electrolyte. The ratio of nickel to copper in the deposits decreased with the distance away from the substrate and the more chloride ions in the electrolyte led to the more nickel content throughout the deposits. Compositional analysis for the cross section of a ramified branch, together with tactical selective copper etching, proved that the copper content increased with approaching central region of the cross section. Such a composition gradient actually disappeared after heat treatment. It is anticipated that the pore gradient nickel-copper nanostructured foams presented in this work might be a promising option for the high-performance electrode in functional electrochemical devices.