Six new anionic bismuth-oxido clusters containing trifluoroacetate ligands were prepared. These include two new Bi6O8 clusters: [M(NCMe)2(H2O)4]3[Bi6(μ3-O)4(μ3-OH)4(CF3CO2)12] with an octahedral Bi6O4(OH)4 core (M = Ni, 1a; Co, 1b) and four Bi4O2 clusters, {[Co(NCMe)6][Bi4(μ3-O)2(CF3CO2)10]}n (2a), {[Co{HC(MeCO)2(MeCNH)}2][Bi4(μ3-O)2(CF3CO2)10]·2[CF3CO2]·2[CF3CO2H]·2[H2O]}n (2b), {[Cu(NCMe)4]2[Bi4(μ3-O)2(CF3CO2)10]·2[CF3CO2H]}n (2c), and {[Me4N]2[Bi4(μ3-O)2(CF3CO2)10]·2[CF3CO2H]}n (2d). These are among the first bismuth-oxido anionic clusters synthesized, and the first to have transition metal countercations. The Bi6O8 anion in 1a and 1b is a high-symmetry octahedron. Additionally, two of the new Bi4O2 clusters are arranged in 1D polymeric structures via bridging carboxylate ligands. The cation in compound 2c had not been previously characterized and was also observed in the synthesis of [Co{HC(MeCO)2(MeCNH)}2][Bi(NO3)6] (3). The new compounds were characterized using single crystal X-ray crystallography and elemental analysis.