The reactions of [M(aet)2] with Pd(II) in water, followed by the addition of NaBr, gave a new class of S-bridged hexanuclear complexes [Pd2{M(aet)2}4]Br4.6H2O (aet = aminoethanethiolate; M = Ni(II) (1), Pd(II) (2)). The same reaction of [Pd(aet)2] With Ni(II) led to the formation of a mixture of S-bridged hexanuclear complexes [Pd2{Ni(aet)2}x{Pd(aet)2}4-x]Br4.6H2O(x = 0-4)(3), which implies that the didentate-N,S ligand aet readily transfers from the Pd(II) to the Ni(II) coordination sphere. The crystal structures of 1-3 were determined by X-ray crystallography : [Ni4Pd2(C2H6NS)8]Br4.6H2O (1), triclinic, P1BAR, a = 11.094(3) angstrom, b = 11.198(3) angstrom, c = 10.937(4) angstrom, alpha = 101.00(2)-degrees, beta = 117.18(1)-degrees, gamma = 71.40(3)-degrees, V = 1143.9(7) angstrom3, Z = 1, and R = 0.048; [Pd6(C2H6NS)8]-Br4.6H2O (2), triclinic, P1BAR, a = 11.212(3) angstrom, b = 11.278(3) angstrom, c = 10.951(4) angstrom, alpha - 101.78(2)-degrees, beta = 116.78(2)-degrees, gamma = 71.21(3)-degrees, V = 1168.8(7) angstrom3, Z = 1, and R = 0.033; [Ni2Pd4(C2H6NS)8]Br4.6H2O (3), triclinic, P1BAR, a = 11.170(4) angstrom, b = 11.240(3) angstrom, c = 10.963(4) angstrom, alpha = 100.85(2)-degrees, beta = 117.02(1)-degrees, gamma = 71.30(3)-degrees, V = 1160.0(7) angstrom3, Z = 1, and R = 0.046. In these complexes, two Pd(II) ions are spanned by four cis(S)-[Ni(aet)2] and/or cis(S)-[Pd(aet)2] units, forming an C4h symmetrical S-bridged hexanuclear structure composed of six square planes. The electronic absorption and C-13 NMR spectral behavior of these complexes is also reported.