The electrochemical behaviour of an Os (II) complex of the structurally well-defined conjugated polymer alternating regioregularly alkylated thiophene and 2,2'-bipyridine units (P4Os) has been elucidated in aqueous solution. In typical aqueous electrolyte systems, the cyclic voltammogram of the resulting P4Os film exhibits a one-electron reversible process corresponding to the Os3+/2+ redox system. However, the observance of this reversible couple did depend upon the concentration of the supporting electrolyte. It was found that the Os3+ form did form ion-pairs with an anion from the electrolyte solution. Preliminary investigations into the homogeneous charge transport dynamics associated with this redox couple have been undertaken. The technique of cyclic voltammetry, and hence the Randles-Sevick expression, in conjunction with platinum microelectrodes have been employed to determine the root DCTC value. (c) 2005 Elsevier Ltd. All rights reserved.