Abstract: A Mn-based coordination polymer (pyH)₂Mn₃(1, 4-NDC)₄·4H₂O (1) (1, 4-NDCH₂=1, 4-naphthalenedicarboxylic acid, py=pyridine) has been solvothermally synthesized and characterized. Single-crystal X-ray diffraction analysis reveals that 1 crystallizes in the noncentrosymmetric space group Cc with a=1.172 45(3) nm, b=3.063 50(8) nm, c=1.439 58(4) nm, β=95.155(3)°, V=5.149 8(2) nm³, Z=4.The adjacent Mn(II) ions are bridged by the -OCO^- groups and μ₂-O(carboxylate oxygen atoms), forming an infinite 1D chain. Each 1D chain is connected to adjacent four 1D chains through the 1, 4-NDC ligands, giving rise to a 3D framework.TGA reveals that lattice water molecules in the channels can be completely removed by heating and the framework is not destroyed.