Synthesis, structural, and magnetochemical characterization of the tetranuclear [Ni4O4] heterocubane cluster [NiCl(L1)(MeOH)]4, 1, employing the bidentate N,O-ligand 2-hydroxymethyl-2-oxazoline, HL1, is reported. In the solid state, each nickel(II) is coordinated in a distorted octahedral environment, located on four corners of a [Ni4(μ3-O)4] cubane core motif. Measurements of the magnetic susceptibility in solution (Evans method) as well as in the solid state (magnetic susceptibility balance) gave values of 5.74 and 6.08 unpaired electrons, respectively, indicating a spin ground state of S = 3. At maximum spin degeneracy (S = 4), eight unpaired electrons would be expected. Magnetic properties were further evaluated by SQUID measurements of 1, confirming the spin ground state of 1 to be S = 3. The observed deviation is caused by antiferromagnetic coupling between the four Ni atoms. In addition, broken-symmetry DFT calculations confirmed an overlap of magnetic orbitals resulting in exchange coupling between the four nickel(II) ions of 1.