Single crystals of a bismuth-based coordination polymer (CP) with carboxyl-thiol ligands, [Bi(C₈H₂O₄S₂)(C₂H₈N)]_n (Bi-DSBDC-DMA, DMBDC = 2,5-disulfur-1,4-dicarboxylate, DMA = dimethylamine), have been successfully synthesized. X-ray diffraction analysis reveals that Bi-DSBDC-DMA possesses a layered structure, with two-dimensional (2D) Bi-DSBDC networks alternating with layers composed of dimethylamine ions. This material demonstrates semiconducting properties, featuring an optical bandgap of 2.2 eV and an electrical conductivity of 2 × 10⁻⁸ S/cm. Furthermore, electrodes based on this material exhibit a capacity of 250 mAh/g after 200 cycles for lithium-ion storage.