According to the “spacer” strategy we have previously proposed the monomers candidate for providing conductive polymers endowed with special properties should contain the polymerogenic rings (pyrrole or thiophene), as terminal units, linked to a central π-conjugatively active frame; we describe how it is possible in this way to control the redox potentials E of the polymers derived from such monomers. This control is beneficial because it is possible to increase the E° value of polypyrrole-type systems and decreases the E° value of polythiophene-type systems. Also, the “spacer”may be further functionalised and, being remote from the polymerisation site, cannot alter the conductivity characteristics typical of the polymer derived from the parent heterocycle (pyrrole or thiophene): such a functionalisation may provide the final, tailored, conductive polymer with special properties (e.g. solubility). If the central ring, acting as a spacer, is formed linking two positions of a di-heterocycle with a saturated chain, it is possible to partially control the twist angle between the heterocyclic units. Crystal and molecular structures have shown that dipyrrole units further linked through the nitrogen atoms are quite sensitive to the central ring size. With respect to the conductivity of unsubstituted polypyrrolc, the conductivity of the polymers derived from such monomers is dependent from the twist angle between the rings. This result is relevant to describe conditions of conjugation between the heterocyclic units of a monomer required to produce upon doping a conductive polymer.