A series of various tris(2,2'-bithiophen-5-yl)-aromatic derivatives were synthesized by Stille cross-coupling procedure. Their structures were characterized by H-1 NMR, C-13 NMR, and elemental analysis. DFT calculations for monomers were also performed. The optical properties of the synthesized materials as well as their energy levels were investigated by UV-vis absorption supported by fluorescence spectra and CV analysis. Oligomers obtained in the process of electropolymerization, possess a tetrathienyl bond with various aromatic and heteroaromatic cores. Electrochemical results confirm that the gained materials can apply successfully for a diversity of organic-electronic devices like organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs), and organic solar cells. (C) 2012 Elsevier Ltd. All rights reserved.