A new binuclear Zn(II) complex, [Zn2(PhBIMP)(DMF)2]3+ (1) (where PhBIMP1 is the anion of 2,6-bis[bis[(N-1-methyl-4,5-diphenylimidazoylmethyl)amino]methyl]-4-methylphenol), has been shown for the first time to mediate the hydrolytic C-S bond cleavage of a series of aliphatic and aromatic thiolates to yield the corresponding alcohols/phenols along with the formation of a hydrosulfide-bridged complex, [Zn2(PhBIMP)(μ-SH)(DMF)]2+ (2), which has been thoroughly characterized in comparison with the corresponding chloride complex, [Zn2(PhBIMP)(Cl)(DMF)]2+ (3), as a control. The binuclear Zn(II)-thiolate complexes [Zn2(PhBIMP)(μ-SR)]2+ (R = Ph, 4a; 3-Br-C6H4, 4b) have also been synthesized by avoiding the C-S bond cleavage reaction. Based on the experimental results for the effects of H2O and Et3N on 1, 4a, and 4b, the complex [Zn2(PhBIMP)(μ-SR)(OH)]1+ has been proposed to be the active intermediate that precedes the C-S bond cleavage of thiolates. The complex [Zn2(PhBIMP)(μ-SCOPh)(DMF)]2+ (5) also demonstrates the hydrolysis of the coordinated thiobenzoate to produce [Zn2(PhBIMP)(μ-O2CPh)(MeCN)]2+ (6). However, unlike 4a and 5, the benzeneselenolate-bridged complex, [Zn2(PhBIMP)(μ-SePh)]2+ (7), does not generate the species, [Zn2(PhBIMP)(μ-SePh)(OH)]1+, in solution, and in line with that, the coordinated benzeneselenolate in 7 does not undergo hydrolysis to generate hydroselenide and phenol. Finally, a comparative study for the transfer reactivity of the bridging -SH, -SPh, -SC(O)Ph, and -SePh ligands in 2, 4a, 5, and 7, respectively, toward selected organic substrates has been performed to reveal the distinct differences in the reactivity of these bridging ligands.