Composite electrochemical coatings (CECs) based on nickel-chromium alloy and modified with multilayer graphene oxide (GO) were obtained. The electrodeposition process of these coatings was studied in the potentiodynamic mode. The structure and the composition of nickel–chromium–GO CECs were studied by scanning electron microscopy and laser microspectral analysis. Nickel–chromium–GO CECs are dense and uniform. The carbon content in them increases when moving from the substrate to the surface. It was established that the addition of GO particles into the composition of electrolytic coatings with a nickel-chromium alloy results in the increase in their microhardness from 4423–5480 MPa to 6120–7320 MPa depending on the cathodic current density.