Abstract 1, n-Di(9-ethylcarbazol-3-yl)alkanes, where n = 1–5, as the dichromophoric model compounds of poly-3-vinylcarbazoles were synthesized to examine their complexation behaviors with the electron acceptors tetracyanoethylene (TCNE) and tetranitromethane (TNM). 9,9′-Diethyl-3,3′-dicarbazolyl, di(3-ethylcarbazol-9-yl)methane, and three monomeric analogues were also included for comparison. In dichloromethane solution, the dicarbazoles formed stable 1:1 electron donor–acceptor complexes with TCNE having formation enthalpies around −3.5 kcal/mol. With TNM they formed more weakly bound complexes that showed little dependence on concentration and almost zero dependence on temperature changes having nearly 0 kcal/mol enthalpies of formation. The smaller gap between the two carbazole groups in 1, n-di(9-ethylcarbazol-3-yl)alkanes with n ≤ 2 affected complexation adversely, while such an effect was not observed in the dicarbazoles with n ≥ 3.