Novel thienyl-dibenzothiophene oligomers end-capped by hexylphenyl groups, 2,8-bis[5-(4-n-hexylphenyl)-2-thienyl]dibenzothiophene (28HPTDBT) and 3,7-bis[5-(4-nhexylphenyl)-2-thienyl]dibenzothiophene (37HPTDBT),have been synthesized using Stille cross-coupling reactions. Newly synthesized oligomers were investigated by Ultraviolet-visible (UV-vis) and photoluminescence (PL) spectroscopy, cyclic voltammogram, and thermal analysis. Strong intermolecular pi-pi interactions, appropriate energy band gaps and low HOMO energy levels imply that the two oligomers are promising candidate materials for durable organic electronic devices.