A series of various tris(2,2′-bithiophen-5-yl)-aromatic derivatives were synthesized by Stille cross-coupling procedure. Their structures were characterized by 1H NMR, 13C 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.