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 ﬁne 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.