Monomers derived from 3,4-ethylenedioxythiophene and phenylenes with branched or oligomeric ether dialkoxy substituents were prepared with the Negishi coupling technique. Electrooxidative polymerization led to the corresponding dialkoxy-substituted 3,4-ethylenedioxythiophene-phenylene polymers, with extremely low oxidation potentials (E-1/2,E-p = -0.16 to -0.50 V vs Ag/Ag+) due to the highly electron-rich nature of these materials. The polymers were electrochromic, reversibly switching from red to blue upon oxidation, with bandgaps at about 2 eV. The electrochemical behavior of the oligomeric ether-substituted polymer was investigated in the presence of different metal ions. Films of the polymer exhibited electrochemical recognition for several alkali and alkaline-earth cations with selectivity in the order Li+ > Ba2+ > Na+ > Mg2+. Cyclic voltammetry showed a decrease in the oxidation potential and an improvement in the definition of the voltammetric response, as well as an increase in the overall electroactivity of the polymer films when the concentration of the cations in the medium was increased. These results are discussed in terms of the electrostatic interactions between the complexed cation and the redox center, as well as the diffusion of the ionic species into the polymer matrix.