The binding ability of a chiral L-cysteinato cobalt(III) complex, [Co(L-cys-N,S)(en)(2)](+) (L-H(2)cys = L-cysteine, en = ethylenediamine), toward a cadmium(II) center, together with the construction of S-bridged (CoCdII)-Cd-III structures that are controlled by anions and pH, is reported. The reaction of Lambda(L)-[Co(L-Hcys-N,S)(en)(2)](ClO4)(2) having a pendent COOH group with CdCl2 in a 1:1 ratio in water, followed by the addition of NaCl, gave an S-bridged (CoCdII)-Cd-III dinuclear complex, Lambda(L)-[CdCl4{Co(L-Hcys-N,S)(en)(2)}](1(Cl)), in which a cadmium(II) ion is weakly coordinated by a thiolato group from a Lambda(L)-[Co(L-Hcys- N, S)(en)(2)](2+) unit, besides four Cl- anions. The corresponding 1:1 reaction with CdBr2 and NaBr yielded an S-bridged (CoCdCoIII)-Cd-III-Co-II trinuclear complex composed of an S-bridged (CoCdCoIII)-Cd-III-Co-II trinuclear cation and a [CdBr4](2-) anion, (Lambda(L))(2)-[CdBr3{Co(L-Hcys-N,S)(en)(2)}{Co(L-cys-N,S)(en)(2)}][CdBr 4](2), while a (CoCdII)-Cd-III dinuclear complex analogous to 1(Cl), Lambda(L)-[CdBr4{Co(L-Hcys-N,S)(en)(2)}](1(Br)), was obtained by the addition of HBr instead of NaBr. In the (CoCdCoIII)-Cd-III-Co-II cation of 2, a Cd-II center is very weakly coordinated by two thiolato groups from Lambda(L)-[Co(L-Hcys-N,S)(en)(2)](2+) and Lambda(L)-[Co(L-cys-N,S)(en)(2)](+) units, besides three Br- anions, with the trinuclear structure being sustained by an intramolecular COOH center dot center dot center dot OOC hydrogen bond. On the other hand, no S-bridged structure was obtained by the corresponding 1:1 reaction with Cdl(2) and Nal, giving only a mononuclear Co-III species with a [Cdl(4)](2-) counteranion, Lambda(L)-[Co(L-Hcys-N,S)(en)(2)][Cdl(4)](3). When Lambda(L)-[Co(L-cys-N,S)(en)(2)]ClO4 having a deprotonated pendent COO-group was reacted with CdCl2 in a 1:1 ratio in water, followed by the addition of NaCl, a one-dimensional ((CoCdII)-Cd-III)(n) polymeric complex, (Lambda(L)) n-[CdCl3{Co(L-cys-N,S)(en)(2)}](n) (4(Cl)), in which Lambda(L)-[Co(L-cys-N,S)(en)(2)](+) units are alternately linked by [CdCl3](-) moieties through thiolato and carboxylate groups, was constructed. An analogous ((CoCdII)-Cd-III)(n) polymeric structure having [Cd(NCS-N)(3)](-) moieties, (Lambda(L)) n-[Cd(NCS-N)(3)-{ Co(L-cys-N,S)(en)(2)}](n) (4(NCS)), was also produced by the use of Cd(ClO4)(2) and NaSCN.