Poly(4,4'-oxydianiline) (poly-ODA) films have been electrochemically deposited onto gold electrodes using cyclic voltammetry. These conducting, electrodeposited films have electrochemical and structural properties that are strongly dependent upon a number of parameters, including the nature of solvent, supporting electrolytes, and the scanning rates. The progress and mechanism of polymerization as well as the structural characteristics of these films were studied using cyclic voltammetry and Fourier transform infrared spectroscopy. A study of the influence of solvophobic interaction between anions and the hydrocarbon radical cation was conducted using a range of solvents having different electron-acceptor/donor properties. The conductivity of the poly-ODA film prepared using tetrahydrofuran was 3.7 x 10(-5) S cm(-1). A possible electropolymerization mechanism is proposed involving the diradical-dication coupling of 4,4'-oxydianiline monomers. (c) 2005 The Electrochemical Society.