A new electroactive polymer with alternating conjugated–nonconjugated repeating units in the main chain was synthesized by step growth polymerization of α,ω-bis(N-carbazolyl)octane in chloroform solution with excess of iron trichloride, and in the presence of N-ethylcarbazole as a terminating agent. The resulting α,ω-N-ethylcarbazole terminated poly(3,3′-bicarbazyl-N,N′-octylene)s are readily soluble in common organic solvents and have good film-forming capabilities, partly because of the special design of the polymer backbone constituted by stiff bicarbazyl chromophores linked by flexible eight-carbon segments. Soluble materials with molecular weights up to 105 g/mol and polydispersity indices around 3.3 were obtained. Purified samples exhibiting quite low polydispersity indices (in the range 1.5–1.7) can be prepared by a selective fractionation of the crude polymer from benzene/methanol mixtures. Structural analysis of these new ‘stairs-like’ polymers disclosed their well-defined character with an aromatic linkage exclusively at position 3 on the carbazole moieties. Electrochemical studies of polymer films exhibited two reversible redox processes between 0 and 1.5 V vs saturated calomel electrode. The photoluminescence (PL) of the polymer in solution and as cast films revealed an intense blue emission and the same intensity level than that of the N,N′-diethyl-3,3′-bicarbazyl molecule, taken as a model of the aromatic segment of the repeating unit. Such a processable and purifiable polymer with bicarbazyl-isolated fluorophores is quite promising for the fabrication of efficient blue light-emitting devices.Read less <