Wet chemical synthesis of silver cables wrapped with polypyrrole is reported in aqueous media without use of any surfactant/capping agent and/or template. The method employs direct polymerization of pyrrole in an aqueous solution with AgNO3 as an oxidizing agent. The four probe conductivity results for the as‐synthesized silver nanocables of polypyrrole films were found to be 3, 5, 5, and 9 S · cm−1 for a 1: 2, 1: 1, 1: 0.5, and 1: 0.1 silver‐to‐pyrrole ratio, respectively. This approach can be extended to other monomers such as aniline and N‐methylaniline (NMA) to prepare different morphologies of silver nanostructures. Aniline monomer polymerization occurred at room temperature to produce a coating of a silver mirror on the side walls of the glass vial, as in the case of Tollen's process of making silver mirrors. The silver mirror coating strategy was extended to a poly(ethylene terephthalate) (PET) surface and the resistivity of the polyaniline‐coated Ag nanocomposites were measured and found to be semiconducting.