Four electrochemical methods, cyclic voltammetric deposition, potentiostatic electrodeposition, multi-potential step electrodeposition and three-step electrodeposition, were used to fabricate Au micro/nanostructures on self-doped polyaniline nanofibers-coated glassy carbon electrodes (Au/nanoSPAN/GCEs). The Au micro/nanostructures deposited on the nanoSPAN-modified electrodes were shown by scanning electron microscopy to exhibit different morphologies, such as Au nanoparticle clusters, monodisperse nanoparticles and homogeneously dispersed flower-like microparticles, depending on the deposition method. This phenomenon demonstrates that control over the morphology of Au metal can be easily achieved by adjusting the electrodeposition method. The electrochemical behaviors of the Au/nanoSPAN/GCEs also varied with above four methods, which were characterized by cyclic voltammetry and electrochemical impedance spectroscopy. In comparison with Au nanoparticle clusters and monodisperse Au nanoparticles, homogeneously dispersed flower-like Au microparticles had the largest surface area and obviously enhanced electrochemical response towards the redox reactions of [Fe(CN) 6 ] 3-/4-on the modified electrode. DNA immobilization on the Au/nanoSPAN/GCEs was investigated by differential pulse voltammetry using [Fe(CN) 6 ] 3-/4-as an indicator. The efficiency of DNA immobilization was inherently related to their different Au micro/nanostructure morphologies. The Au/nano-SPAN/GCE fabricated by three-step electrodeposition showed the largest capacity for immobilization of single stranded DNA, which makes it a promising DNA biosensor. electrodeposition, Au micro/nanostructure, polyaniline nanofiber, DNA immobilization Citation:Wang X X, Yang T, Jiao K. Controllable fabrication of Au micro/nanostructures on self-doped polyaniline nanofibers via electrochemical deposition and its application for DNA immobilization.