Multilayer electroforming has a high potential to produce Ni/Ni layer structured metal walls with excellent material properties and a high thickness uniformity. However, Ni is easily oxidized in air, which fundamentally leads to a low adhesion strength between the Ni layers. Here, a novel in situ treatment is proposed for improving the adhesion performance between Ni layers. This treatment integrated the steps of electrochemical dissolution, surface protection, and electroforming. A study of the polarization behavior implied the electroformed Ni layer was dissolved efficiently in the NH2SO3H solution, beginning at a dissolution current density of 5 A·cm−2, which could remove the oxide film. A smooth substrate surface with a good surface hydrophilicity was obtained starting at 8 A·cm−2, helping to protect the activated substrate from being contaminated and oxidized. The experimental results showed that ultrahigh normal and shear adhesion strengths over 400 MPa between the Ni layers were achieved.