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]H2 ligand precursor reacted with titanium(IV) isopropoxide and with zirconium(IV) tert-butoxide to give the corresponding [OSSO]-M(OR)2 complexes, which formed as single C2-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 C2 symmetry.