A synthesis strategy for the manufacture of inexpensive highly efficient nanostructured catalysts has been developed. The developed unique nonplatinoid copper-based catalysts with different surface morphology were investigated as a functional layer with high activity in the ethanol oxidation in alkaline media. A modifying layer with controlled morphology, composition, and excellent electrocatalytic activity was synthesized by electrochemical deposition by varying such synthesis parameters as deposition temperature and time, concentration of structure-forming additives, and electrodeposition current. The dependence of the samples’ electrocatalytic activity on the shaping factors was established. According to the electrochemical study results, the highest current density peak of up to 33.01 mA cm−2, and hence the highest catalytic activity in comparison to other samples, were possessed by a catalyst with a regular cubic particle shape. A catalyst consisting of plate-like nanoparticles with a certain percentage of disclinations had similar, but slightly less activity, with a current density peak of up to 31.59 mA cm−2. The samples’ activity values are 8 times higher for cubic particles and 7.5 times higher for particles with a triangular plate shape than for an unmodified smooth copper film. The developed samples can be considered as quite competitive to platinoid catalysts, which significantly outperform copper analogues.