A strategy to decrease the bandgap of polypyrrole in modified pyrrole-based polymers is the alternation of acceptor (A) and donor (D) groups in the chain. The synthesis of appropriate monomers, their electropolymerization to polyconjugated conducting polymers, and evidence for the narrow bandgap properties of the corresponding neutral systems are described. It is demonstrated that in the presence of specific charge-transfer interactions between the A and D groups the decrease in the bandgap is strongly enhanced.