Oligo(thienylphenyl)amine (TTPA) derivatives which have different thiophene units and potential gradient molecules were synthesized. From the investigation of steady‐state absorption and emission properties and the estimation of the free energy and the energy level of the oligomers, the energy transfer efficiency of the oligomers increased with increasing thiophene units, implying that the energy transfer mainly occurs through space due to a large area overlap existing between the absorption and the emission spectra of the oligomers. Furthermore, based on the calculated Rehm‐Weller equation (ΔGen and ΔGel) and energy diagrams of the oligomers, we found that 4TTPA ( 4 ), having a 4‐unit thiophene in the backbone, showed higher energy transfer efficiency compared to that of the others.
