The first high nuclearity, mixed-metal Bi-III/Mn-IV and Bi-III/Mn-III complexes are reported. The former complexes are [(Bi2Mn6O9)-O-IV(O2CEt)(9)(HO2CEt)(NO3)(3)] (1) and [Bi2MnIV O-6(9) (O2CPh)(9) (HO2CPh)(NO3)(3)] (2) wad were obtained from the comproportionation reaction between Mn(O2CR)(2) and MnO4- in a 10:3 ratio in the presence of Bi(NO3)(3) (3 equiv) in either a H2O/EtCO2H (1) or MeCN/PhCO2H (2) solvent medium. The same reaction that gives 2, but with Bi(O2CMe)(3) and MeNO2 in place of Bi(NO3)(3) and MeCN, gave the lower oxidation state product [BiMnIII O-10(8)(O2CPh)(17)(HO2CPh)(H2O)] (3). Complexes 1 and 2 are near-iso-structural and possess an unusual and high symmetry core topology consisting of a Mn-6(IV) wheel with two central Bi-III atoms capping the wheel on each side. In contrast, the [BiMnIII O-10(8)](17+) core of 3 is low symmetry, comprising a [BiMn3(mu(3)-O)(2)](8+) butterfly unit, four [BiMn3(mu(4)-0)](10+) tetrahedra, and two [BiMn2(mu(3)-O)](7+) triangles all fused together by sharing common Mn and Bi vertices. Variable-temperature, solid-state dc and ac magnetization data on 1-3 in the 1.8-300K range revealed that 1 and 2 possess an S = 0 ground state spin, whereas 3 possesses an S = 2 ground state. The work offers the possibility of access to molecular analogs of the multifunctional Bi/Mn/O solids that are of such great interest in materials science.