Phenylenediamine (PDA) was chosen as a coordinating, reducing, and capping agent to effectively direct growth and protect against oxidation of Cu nanowires (Cu NWs) in an aqueous solution. PDA was found to reduce Cu (II) to Cu (I) at room temperature, and stabilize the resulting Cu (I) by forming a coordination complex. The presence of a stable Cu (I) complex is the key step in the synthesis of Cu NWs under mild conditions. Different PDA isomers lead to different growth paths of forming Cu NWs. Both pPDA and mPDA-synthesized Cu NWs were covered with a thin layer of polyphenylenediamine and show excellent anti-oxidation properties, even in the presence of water. The usefulness of the present and electrochemical active Cu NWs for a variety of nanotechnology applications is discussed.