This study investigates the corrosion behavior of the nickel/nickel (Ni/Ni) interface during the release of the copper-sacrificial layer in multilayered micro-electroforming. By altering the pre-and posttreatment of multilayered micro-electroforming (degreasing, in situ anodic treatment, pickling, repassivation, and heat treatment), six different types of Ni/Ni interfaces were obtained. The activities and surface characteristics of the pretreated Ni substrates were investigated via open circuit potential and X-ray photoelectron spectroscopy. The microstructures of the as-prepared Ni/Ni interfaces were determined using scanning electron microscopy; after releasing the sacrificial layer in the ferric chloride solution, their corrosion morphologies and corrosion depths were observed under a three-dimensional microscope with an ultra-depth of field. The Ni/Ni interface showed a pre-existing passive layer and interfacial defects. The interface was more prone to attack than the Ni base. Pitting corrosion along the interface boundary occurs via three main processes-initiation, growth, and pit coalescence-with a corresponding reduction in the interfacial adhesion strength and ultimately the structural integrity. The combination of substrate modification (degreasing and pickling) and heat posttreatment effectively avoids localized corrosion. We believe that the surface activation and thermally induced diffusion have worked.