Triphenylamines with thienyl groups are electro-oxidatively polymerized to yield the corresponding branched polymers on an electrode. The resulting polymers show significantly better redox properties, such as redox activity, catalytic activity, and conductivity when compared with for example the linear polymeric analog. The good properties of the branched polymers are based on the higher electronic conductivity (2-6 S/cm), since the branching provides multiple routes for charge carriers. The redox-active polymers show high capacity (ca, 40 mC/cm(2)) and catalytic activity for the electron transfer of ferrocene on the electrode.