The synthesis of a novel complex [Ni₃(L^3-)₂(1,4-bib)₄(H₂O)₂]·5H₂O (1) with three-dimensional framework structure was achieved through a hydrothermal reaction, employing 5-((4-carboxylphenoxy)-methyl) isophthalic acid (H₃L) as the main oxygen-containing ligand, complemented by the N-donor ligand 1,4-bis(1H-imidazol-1-yl)benzene (1,4-bib), and Ni(II) ions. The structure of complex 1 was characterized by single crystal X-ray diffraction, powder X-ray diffraction, and elemental analysis. Complex 1 is crystallized in the triclinic crystal system of P-1 space group, and its crystallographic parameters are a=1.260 5(7) nm, b=1.349 1(7) nm, c=1.364 8(7) nm, α=111.913(8)°, β=117.251(7)°, γ=90.732(8)°, V=1.866 2(18) nm³, Z=1, M_r=1 769.66, F(000)=916, μ=0.84 mm^-1, D_c=1.575 mg·m^-3, S=1.06, R₁=0.056, wR₂=0.159. The joint contribution of semi-rigid tricarboxylic acid ligand L^3-, rigid 1,4-bib and also with Ni(II) ion to form a predictable high-dimensional structure. Complex 1 is a three-dimensional network constructed through the coordination of N and O atoms with Ni ion and the structural extension of the ligand. In addition, the magnetic properties of Ni(II) compound containing single d electron center were studied: the carboxyl group in mononuclear complex 1 only binds to one cation, resulting in magnetism in the solid being determined by the behavior of single metal ions. Variable temperature magnetic susceptibility of χ_mT in complex 1 can be described by zero field splitting.