A straightforward synthesis of a new type of tetradentate dianionic [OSSO]-type ligand is described. This ligand features an ethylenedithiol core bridged via methylene groups to substituted phenols, thus representing an S analogue of the [ONNO]-type Salan ligands. The [OSSO]H-2 ligand precursor reacted with titanium(IV) isopropoxide and with zirconium(]V) tert-butoxide to give the corresponding [OSSO]-M(OR)(2) complexes, which formed as single C-2-symmetric isomers but were fluxional according to variable-temperature NMR. An X-ray structure of [OSSO]-Zr(O-t-BU)(2) supported the fac-fac wrapping mode of the ligand. The dibenzyl complex [OSSO]-Zr(bn)(2) that was obtained by a reaction between the ligand precursor and tetrabenzylzirconium was found to be an active 1-hexene polymerization catalyst upon activation with B(C6F5)(3), leading to a stereoirregular polymer despite its C-2 symmetry.