This work focuses on the development of novel six-membered polyimides, with special concern on the effect of the structural variation on their optoelectronic characteristics and electrochromic performances in electrochromic devices. To this aim, a new aromatic diamine incorporating diphenylamine substituted at the nitrogen atom with a 2-(4-methoxyphenyl)-1,3,4-oxadiazole segment was synthesized and fully characterized. This diamine was used in the one-step high-temperature polycondensation reaction with naphthalene- or perylene-based dianhydrides to produce highly conjugated polyimides. To highlight the effect of structural variation in the diamine segment on the main physical properties, {4-[-5-(4-fluorophenyl)-1,3,4-oxadiazol-2-yl]-phenyl}-bis-(4-amino-phenyl)-amine was reacted with the same dianhydrides to obtain related polyimides. The obtained polymers displayed high thermal stability, up to 423 degrees C, and could be processed into thin coatings with morphologies contingent on the macromolecular architecture. With the ability to promote a dual intramolecular charge transfer complex between the diphenylamine/triphenylamine unit and both 1,3,4-oxadiazole in the side chain and naphthylimide or peryleneimide in the main chain, these polyimides experienced challenging photo-optical properties, which were driven by the competition between the electronic effects. The HOMO-LUMO energies evaluated from cyclic voltammetry experiments suggested ambipolar electronic transport characteristics, with a prevalent n-doping capability. Since the oxidation processes of perylene-based polyimides were accompanied by color switching between neutral and oxidized states, preliminary testing in electrochromic devices was carried out. Besides the stable anodic coloring with good response times, the recovery of electrochromic devices was similar to 90% after 30 cycles. This excellent stability is mainly promoted by the more extended conjugation provided by the peryleneimide system.