Four new Ni-substituted Krebs-type sandwich-tungstobismuthates, K4Ni2[{Ni(β-ala)(H2O)2}2{Ni(H2O)}2{Ni(H2O)(η2-β-ala)}2(B-β-BiW9O33)2]·49H2O {(β-ala)4(Ni3)2(BiW9)2}, K3.5Na6.5[{Ni(η3-L-asp)}2(WO2)2(B-β-BiW9O33)2]·36H2O·L-asp {(L-asp)2(NiW)2(BiW9)2}, K4Na6[{Ni(gly)(H2O)2}2(WO2)2(B-β-BiW9O33)2]·86H2O {(gly)2(NiW)2(BiW9)2}, and K2Na8[{Ni(η2-serinol) (H2O)}2{Ni(H2O)2}2(B-β-BiW9O33)2]·42H2O {(serinol)2Ni4(BiW9)2} have been synthesized by one-pot solution methods. All compounds have been characterized in the solid state by single-crystal X-ray diffraction (SXRD), powder X-ray diffraction (PXRD), elemental and thermogravimetric analyses, and infrared spectroscopy (IR), as well as by UV-vis spectroscopy in solution. The antibacterial activity of all compounds was studied against four bacterial strains by the determination of the minimum inhibitory concentration (MIC). The results showed that only {(β-ala)4(Ni3)2(BiW9)2} demonstrates antibacterial activity (MIC is in the range from 8 to 256 μg/mL) compared to three other Ni-Krebs sandwiches.