A new coordination polymer [Ni(L)(bib)]n (H2L=5-hydroxyisophthalic acid, bib=1,4-bis (2-methyl- imidazol-1-yl)butane) has been prepared by hydrothermal synthesis and characterized by single-crystal X-ray diffraction, IR, and elemental analysis. The crystal is of monoclinic, space group P2(1)/n with a = 8.949(4), b = 20.620(9), c = 10.945(5)Å, β = 103.642(5)°, C20 H22 N4 NiO5. Mr = 457.11, V = 1962.7(15) Å3, Dc = 1.547 g/cm3, F(000) = 952, µ = 1.030 mm−1, and Z = 4. The final refinement gave R = 0.0244 and wR = 0.0654 for 3227 reflections with I > 2σ(I). The analytic conclusions reveal that the carboxylate groups adopt chelating coordination mode, which lead to form a 1D chain. The 1D chain is further connected by the bib ligand to form 2D layer. Through hydrogen bonding interactions, the 3D supramolecular structure is formed with InS topology.