Optoelectronic devices fabricated from organic low-molar-mass and polymeric materials are gaining recognition and attention of the electro-optical industrial community. The most widely used building blocks of hole-transporting polymers and molecular glasses are aromatic amino groups and carbazolyl group in particular. Carbazolyl fragment is interesting as a building block in the design and synthesis of electroactive materials for the following reasons: (1) carbazole is rather cheap starting material; (2) it is a fully aromatic unit providing a good chemical, electrochemical and environmental stability; (3) it can be easily substituted with a wide variety of functional groups to help the solubility and to tune the optical and electrical properties. [3,3?]Bicarbazolyl unit is much less studied and used in the design and synthesis of organic semiconductors and other electroactive materials. New macromolecular and low-molar-mass charge-transporting compounds containing [3,3?]bicarbazolyl and aromatic amino moieties with different arylamino groups as substituents have been synthesized. The thermal, optical and photoelectrical properties of the obtained materials have been studied.