The metal iodides reduce partially the host coordination polymer of the type 3¥ [ ( extMe 3 extSn ) 3 extFe( extCN ) 6 ] , I, to give new host–guest supramolecular coordination polymers (SCP). The physical and chemical characteristics of the new products were studied by elemental analyses, X-ray powder diffraction, IR, UV/Vis, and solid state NMR spectra. The host–guest SCP are [Mx(Me3Sn)3Fe(1–x)IIIFexII(CN)6]n M = Li+·2H2O, 1; Li+, 2; Na+, 3; K+, 4; Cu+, 5, [Li(Me3Sn)3FeII(CN)6]n, 6 and [(LiDEE)0.9(Me3Sn)3Feo.1IIIFeo.9II(CN)6]n, 7. The stoichiometry and nature of the guest depend on the type of the metal iodide and the reaction conditions. The polymeric nature of these SCP is due to the presence of trigonal bipyramidal configured structure which bridges between the single d-transition metal ions. The host–guest SCP containing the Li ions have been tested as electrodes to construct four different lithium-ion batteries.