Polythiophene (PTh)-based coordination complexes, polythiophene-iron (PTh-Fe) and polythiophene-iron-oxygen (PTh-Fe-O) were synthesized by chemical method and proved to be novel high-performance organometallic lithium-storage materials. Extended X-ray absorption 铿乶e structural (EXAFS) spectroscopy and density functional theory (DFT) calculations indicate that these complexes have layered structures. It is believed that the strong and stable Fe-S coordination creates sites of lithium storage and ensures the high specific capacity and outstanding cycle performance of the PTh-based complexes.