A new complex, [Ni2(L)4(H2O)8](1, L1 = 4-(1H-imidazol-4-yl)benzoic acid), has been hydrothermally prepared and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and PXRD. Complex 1 crystallizes in monoclinic, space group P21/c with a = 22.281(2), b = 7.3959(7), c = 24.978(3) ?, β = 90.876(10), V = 4115.6(7) ?3, Z = 8, C20H22N4O8Ni, Mr = 505.13, Dc = 1.630 g/cm3, μ = 1.001 mm-1, S = 1.080, F(000) = 2096, the final R = 0.452 and wR = 0.1152 for 9380 observed reflections(I > 2σ(I)). The result of X-ray diffraction analysis revealed three different kinds of Ni(II) centre mononuclear molecules in the asymmetric unit. The independent mononuclear units are bridged to form a three-dimensional supramolecular polymer by extensive hydrogen bonds and C–H···π non-covalent bonding interactions.