Diamond-incorporated copper metal matrix layers were fabricated on brass substrates by using electrodeposition technology in this study. To improve the adhesion of the composite coatings on the brass substrate, a plated copper was applied as the interlayer between the multilayers and the substrate. The surface morphologies of the interlayer and the diamond-incorporated copper composite layers were studied by scanning electron microscopy. The effect of the copper interlayer on the incorporation and the distribution of the diamond content in the coatings was analyzed by surface roughness, electrochemical impedance spectroscopy, and cyclic voltammetry. The diamond content of the composite coating was measured by energy-dispersive X-ray. The film thickness was evaluated by the cross-sectional technique of focused ion beam microscopy. The element, composition, and crystallization direction of diamond with Cu matrix was measured by X-ray diffraction and transmission electron microscope. The adhesion of the multilayers was studied by scratch tests. The experiment results indicated that the diamond content and distribution of the coating were higher and more uniform with the Cu interlayer than that without one. The plated copper interlayer reduced the electrical double-layer impedance and enhanced the adsorption of diamond particles by the surrounding Cu ions, which promoted the diamond content in the composite coatings. The roughened surface caused by the plated Cu interlayer also improved the substrate’s mechanical interlock with the composite coating, which contributed to the strong adhesion between them.