Sulfur-based heterocycles were one of appealing building blocks in functional materials, due to their outstanding optical/electronical performance. Assembled DTTF-BTh which combined from two different sulfur heterocycles was synthesized by condensation of 2-cyanoethylthio-3-methylthio-6, 7-bis (hexylthio) tetrathiafulvalene ( TTF-1), and 4, 4′-bis (2′-bromoethoxy)- 3, 3′-bithiophene ( DBE-BTh). The full structural and physical characterizations of novel DTTF-BTh were studied by H NMR, Mass, UV-Vis absorption, and electrochemical measurements. The two heterocycle moieties were connected successfully but inclined to perform individually. This could be explained as electron separation by alkyl chains. Electropolymerization was also conducted. The result indicated that DTTF-BTh could directly form polymeric films on prepared ITO glass via electrochemical deposition. Moreover, the deposited polymer film possessed an electrochromic performance. [ABSTRACT FROM AUTHOR]