The use of the [ReCl4(bpym)] precursor as a ligand toward the fully solvated nickel(II) metal ion affords the first example of a 2,2'-bipyrimidine-bridged Re-IV-Ni-II complex, [ReCl4(mu-bpym)NiBr2(H2O)(2)] (1), whose intramolecular ferromagnetic coupling has been substantiated from both experimental and theoretical studies.