Design and synthesis of conjugated organic polymers for electronic and optoelectronic applications, such as electrochromic devices (ECD), organic light emitting diodes (OLED), organic field effective transistors (OFET), lasers, photodiodes and solar cells, have an increasing momentum. Fused thiophenes, i.e. thieno[3,2-b]thiophenes (TT), have been widely accepted as important building blocks for such materials. In this work, 4-thieno[3,2-b]thiophen-3-ylbenzonitrile (TT-CN), having electron withdrawing cyano moiety, was polymerized with anthracene and biphenyl through Suzuki coupling to obtain the polymers. Electronic and optical properties of the resultant polymers were investigated. Effects of different molecular orientations of anthracene and biphenyl blocks in the polymer backbone were compared.