The reaction of RBiCl2 (1) [R = 2,6-(Me2NCH2)2C6H3] with Na2CO3 or Ag2SO4 (1 : 1 molar ratio) gave RBiCO3 (2) and RBiSO4 (3), respectively. RBi(NO3)2 (4) was obtained from RBiCl2 and AgNO3 (1 : 2 molar ratio). The ionic complex [R2Bi][W(CO)5Cl] (6) was obtained from R2BiCl (5) and W(CO)5(THF), following an unusual chlorine transfer from bismuth to tungsten. Compounds 2–4 are partially soluble in water. The molecular structures of 2·0.5CH2Cl2, 3, 4·H2O and 6 were established by single-crystal X-ray diffraction. The carbonate 2 and the sulfate 3 exhibit a polymeric structure based on bridging oxo anions, while for the compound 4 dimer associations are formed, with both bridging and terminal nitrate anions. Dimer associations, based on weak Cl⋯H interactions between the cation and the anion, were found in the crystal of 6.