4,4'-Biimidazole and two kinds of quaterimidazoles were designed and firstly synthesized, aiming at constructing the charge-transfer complexes with the intermolecular hydrogen-bonding interaction. The one-dimensional hydrogen-bonded structure of 4,4'-biimidazole containing protonated 4,4'-biimidazole was confirmed by the crystal structural analysis. TCNQ complexes of the oligoimidazoles exhibited a semiconductive behavior with high conductivity.