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 (Ni 3 ) 2 (BiW 9 ) 2 }, K3.5Na6.5{Ni­(η3-L-asp)}2(WO2)2(B-β-BiW9O33)2·36H2O·L-asp {(L-asp) 2 (NiW) 2 (BiW 9 ) 2 }, K4Na6{Ni­(gly)­(H2O)2}2(WO2)2(B-β-BiW9O33)2·86H2O {(gly) 2 (NiW) 2 (BiW 9 ) 2 }, and K2Na8{Ni­(η2-serinol) (H2O)}2{Ni­(H2O)2}2(B-β-BiW9O33)2·42H2O {(serinol) 2 Ni 4 (BiW 9 ) 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 (Ni 3 ) 2 (BiW 9 ) 2 } demonstrates antibacterial activity (MIC is in the range from 8 to 256 μg/mL) compared to three other Ni-Krebs sandwiches.