The tetranuclear nickel(II) complex of 24-membered Schiff base macrocyclic ligand has been prepared by template condensation of two molecules 2,6-diformyl-4-chlorophenol with two molecules 2,6-bis(aminomethyl)-4-methylphenol monohydrochloride in methanol solution in the presence of excess nickel(II) acetate and sodium acetate/ acetic acid. The tetranuclear nickel(II) complex contains neutral molecules of composition LNi4(CH3COO)2(OH)(CH3O ⋅ H ⋅ OCH3), together with two molecules methanol in the lattice, and it possesses a monoclinic space group C2/c, with a = 21.5053(18) Å, b = 8.8782(7) Å, c = 25.374(2) Å, β = 93.7830(10)°, and Dcalc = 1.631 mg/m3 for Z = 8. The crystallographic data show that the macrocyclic ligand binds four nickel(II) ions at the corners of an approximate square with a μ4 hydroxo group bound equally to four metals.