Copper/lophine core/shell nanocomposites were fabricated through the self-assembly of lophine on the surfaces of copper nanostructures. The growth of the lophine shells was induced by the cooperation of coordination and several other noncovalent interactions. The dimensions, structures, and morphologies of the nanocomposites can be readily controlled by just altering the size and morphology of the copper core. The formation mechanism of the core/shell nanocomposites was put forward on the basis of a series of characterizations. The optical properties of the shell lophine layer can be tuned by changing the size of the copper core.