Several thiophene derivatives containing different heteroatom linkers were rationally designed, synthesized and studied as potential candidates for solid state polymerization (SSP). Due to the flexible short single heteroatom linkers, these monomers may rotate freely under heating to meet the requirement needed for SSP. Meanwhile, our novel design strategy has been proved to be an amazing protocol and will pave the way to explore more systems in the polythiophene family by using such a facile SSP method.