In this paper, electrochemically prepared poly (1,8-diaminonaphthalene) is characterized in terms of its electrochemical, chemical, and electrical properties. The polymer is electroactive in aqueous solutions, has a reasonable conductivity of 2 to 3 S/cm in its doped form, and has free-amine groups as examined by infrared spectra as well as its ability to form a complex with Ag[sup +] in solution. The stripping current of reduced Ag[sup +] complexed onto the polymer is diffusion controlled, indicating that a major fraction of the complexed Ag[sup +] is inside the polymer matrix. When the Ag[sup +] complexed polymer is electrochemically reduced, it increases in conductivity by more than two orders of magnitude compared with that of the fully doped uncomplexed polymer by oxidation. This is a unique technique of doping a conducting polymer containing functional groups such as amines.