Dipyrrolyl monomers with more or less flexible and bulky spacers have been synthesized. The electrochemical behaviour of these monomers and their corresponding polymers has been investigated. Convergent results, obtained by cyclic voltammetry of the monomers and the polymers, ESCA analysis and mass measurements, demonstrate that from an early stage of polymerization, the monomers are oxidized at both pyrrolyl units, leading to different polymer structures, depending on the spacers used.