The design and fabrication of PTh-PPY heterojunction nanowires that exhibits smart responses to electrochemical redox potentials is described. In their oxidized state, PTh-PPY nanowires act as resistors, whilst in their reduced state, they acts as diodes. Furthermore, the electrical transport mode can be reversibly changed by alternately exposing the nanowires to negative and positive potentials. Constructing full-organic heterojunction nanowires with smart, controllable properties will contribute to the development of intelligent organic devices and organic-electronic circuits on the nanoscale.