Graphical Abstract: Dinuclear nickel(II) pivalate with µ-aqua- and di-µ-pivalato-bridges having monodentate pivalato and monodentate pivalic acid molecules, [Ni2{O2CC(CH3)3}4(OH2){HO2CC(CH3)3}4], was prepared and characterized by elemental analysis and IR and UV-Vis spectroscopies, temperature dependence of magnetic susceptibilities (4.5—300K), and single-crystal X-ray crystallography. The magnetic data analysis showed a ferromagnetic interaction between the two nickel atoms.