Manganese-based layered coordination polymer ([Mn(tfbdc)(4,4'-bpy)(H2O)2], Mn-LCP) with microporous structure was synthesized by reaction of 2,3,5,6-tetrafluoroterephthalatic acid(H2tfbdc) and 4,4'-bipyridine(4,4'-bpy) with manganese(II) acetate tetrahydrate in water solution. Mn-LCP was characterized by elemental analysis, IR spectra, thermogravimetric analysis, X-ray single-crystal structure analysis, and powder X-ray diffraction. Magnetic susceptibility data from 300 to 1.8K show that there is a weak antiferromagnetic exchange between Mn(II) ions in Mn-LCP. As anode material, the Mn-LCP electrode exhibits an irreversible high capacity in the first discharge process and a reversible lithium storage capacity of up to about 390 mA h/g from the fourth cycle. It might provide a new method for finding new electrode materials in lithium-ion batteries.