The synthesis of the novel tripodal ligand [N(CH2CH2CH2OH)(CH2CH2SH)(2)] H-3-4 is reported. The aliphatic tetradentate ligand is equipped with an unsymmetrical NOS2 donor set. It reacts with Ni(OAc)(2).4H(2)O or Zn(BF4)(2).xH(2)O to give the complexes [Ni(H-4)](2) 5 and [Zn(H-4)](4) 6, respectively. The molecular structures of 5 and 6 have been determined by X-ray diffraction. In both cases multinuclear, mu-thiolato-bridged complexes, wherein the ligand coordinates with only three (NS2) of the four donor groups, had formed. The dinuclear complex 5 adopts a butterfly geometry and contains nickel(II) ions in a square-planar NS3 coordination environment. Cyclic voltammetry experiments indicate that the nickel centers in 5 are electron-rich but not overly sensitive toward oxidation. Complex 6 is tetranuclear and the four thiolato-bridged metal centers form a ring. It shows a distorted tetrahedral coordination geometry for the zinc(II) ions in an NS3 coordination sphere. In both complexes the hydroxyl functionalized ligand arm of the tripodal ligand remains uncoordinated.