New compounds consisting of two different electropolymerizable aromatic groups (pyrrole/thiophene 1, pyrrole/dimethoxybenzene 2, and dimethoxybenzene/thiophene 3) linked together by a polyether subunit have been synthesized and their electrochemical behavior has been investigated. At relatively low anodic potential values, the oxidation of these monomers led to electroactive homopolymer films containing pendant aromatic moieties. The oxidation of the preformed polymers by applying more positive potentials promoted further anodic couplings within their structure. The efficiency or this solid-state electropolymerization reaction was found to be strongly dependent on the film thickness. So, electroactive copolymers possessing controllable size pseudo-crown ether cavities were thought to be obtained.