The first bottom-up electrochemical approach for the preparation of viologen (1,1′-didodecyl-4,4′-bipyridinium salt) nano/microsized wires and tubes are described. This approach involves film formation of the viologen using the micellar disruption method followed by transformation of the film into the nano/microstructures using a potential sweep technique. The hexagonal cross-section of the wires and tubes has a 400nm–30μm width and >1mm length. The formation mechanism of the nano/microstructures was discussed on the basis of the X-ray photoelectron spectroscopic analyses, FT-IR spectra, scanning electron microscopic observation, UV–vis spectra, and cyclic voltammograms before and after the transformation.