The potentiometric response of some polythiophenes in aqueous solutions has been investigated. Polythiophene (PT), poly(2,2'-bithiophene) (PBT), poly(3-methylthiophene) (PMT), poly(3-octylthiophene) (POT) and poly(4,4'-dioctyl2,2'-bithiophene) (POTd) were electrochemically deposited on platinum in 0.1M LiBF(4)-propylene carbonate solution containing the corresponding monomer or dimer. Polymer electrodes were also prepared by solution casting of chemically synthesized poly(3-octylthiophene) (POTc) dissolved in chloroform. After film deposition (electrochemical or chemical) the polymer coated electrodes were used as indicator electrodes in potentiometric measurements. The open-circuit potential of the polymer electrodes was measured in aqueous solutions containing inorganic salts (10(-1)-10(-4)M). Interestingly, all the polythiophenes studied were found to give a cationic response to monovalent cations such as H(+), Li(+), Na(+), K(+) and NH(+)(4) (Cl(-) salts). The slope, calculated from the linear part of the response curve, was found to depend on the polythiophene used but always remained lower than that predicted for a Nernstian response. The polythiophenes also showed some sensitivity to divalent cations such as Mg(2+) and Ca(2+) (Cl(-)-salts). POT was used as the polymer to study the influence of the polymerization conditions on the potentiometric response. By investigating different polymers from the polythiophene family it was possible to evaluate how the starting material (monomer or dimer) and the presence of alkyl side-chains influence the potentiometric response of the polymer membranes.