Silanization of glass surfaces by (3-glycidoxypropyl)trimethoxysilane (GPS) provided a surface-coupled layer of functional molecules for the subsequent reaction with aniline (An). The so-modified glass surface (the An-GPS-glass surface) was then subjected to oxidative graft polymerization of aniline. The composition and microstructure of the modified glass surfaces were characterized by X-ray photoelectron spectroscopy (XPS), UV-visible absorption spectroscopy, and atomic force microscopy (AFM). The protonation-deprotonation behavior, the interconvertible intrinsic redox states, and the spontaneous metal reduction behavior of the grafted polyaniline (PANI) chains on the glass surface (the PANI-An-GPS-glass surface) were similar to those of the PANI homopolymer. The PANI-An-GPS-glass surface with the electrolessly deposited palladium could be used to catalyze the electroless deposition of copper (the Cu-Pd-PANI-An-GPS-glass surface). The spatial distribution of the grafted PANI chains into the matrix of the electrolessly deposited metals had given rise to the strong adhesion of copper to the glass surface. Adhesion failure occurred at the interface between the copper foil backing and the epoxy adhesive when both were applied onto the Cu-Pd-PANI-An-GPS-glass surface in an attempt to peel off the electrolessly deposited metal layer and the tethered polymer layer from the glass surface.