Abstract: The Steglich esterification has been proved as an effective tool to connect TTF-acid moiety with other valuable structures. ProDOT(CH₂OH)(CH₂O-TTF) and ProDOT(CH₂O-TTF)₂ were designed and synthesized via Steglich esterification (DMAP/DCC) reaction between ProDOT(CH₂OH)₂ and tetrathiafulvalene derivatives. By tuning the ratio of these two substrates, two different monomers were obtained. ProDOT(CH₂OH)(CH₂O-TTF) and ProDOT(CH₂O-TTF)₂ were obtained with yield of 76% and 80%, respectively, when the reaction was performed under the conditions of ProDOT(CH₂OH)₂, TTF-COOH, DCC, DMAP, DCM, room temperature, and reaction time (24 h). Their structures were characterized by HRMS and ¹H-NMR. The optical and electrochemical properties of the two monomers were also studied via UV-vis spectra and cyclic voltammetry. The data indicated that weak ICT effect was presented in the ProDOT(CH₂O-TTF)₂, but not in the ProDOT(CH₂OH)(CH₂O-TTF), and the electrons of two parts were separated. In order to get further insight into the properties of the monomers, molecular simulation based on DFT with Gaussian 03 package (DFT was treated with the B3LYP/6-31G* basis sets) was performed. The calculation results were in line with our speculation, demonstrating that weak ICT effect found in the ProDOT(CH₂O-TTF)₂ might result from the stereo-electronic effect.