We have demonstrated a new and simple methodology to quantify the amount of metallic Ni present in the mixed nickel hydroxide/nickel surface using galvanic replacement reaction. This method was also used to manipulate the formation of nanocomposite, NiPd on Ni(OH)(2) support by controlling the extent of galvanic replacement of Ni by Pd. The bimetallic NiPd nanoparticles supported on Ni(OH)(2) prepared by galvanic reaction showed better electrocatalytic activity for methanol oxidation than commercial Pd/C. This approach can be extended to synthesize various nickel containing bimetallic nanoparticles essential for different catalysis.