Exposing [Bi(OR)(3)(toluene)](2) (1, R = OC6F5) to different solvents leads to the formation of larger polymetallic bismuth oxo alkoxides via ether elimination/oligomerization reactions. Three different compounds were obtained depending upon the conditions: Bi-4(mu(4)-O)(mu-OR)(6){mu(3)-OBi(mu-OR)(3)}(2)(C6H5CH3) (2), Bi-8(mu(4)-O)(2)(mu(3)-O)(2)(mu(2)-OR)(16) (3), Bi-6(mu(3)-O)(4)(mu(3)-OR){mu(3)-OBi(OR)(4)}(3) (4). Compounds 2 and 3 can also be synthesized via an alcoholysis reaction between BiPh3 and ROH in refluxing dichloromethane or chloroform. Related oxo complexes NaBi4(mu(3)-O)(2)- (OR)(9)(THF)(2) (5) and Na2Bi4(mu(3)-O)(2)(OR)(10)(THF)(2) (6) were obtained from BiCl3 and NaOR in THF. The synthesis of 1 and Bi(OC6Cl5)(3) via salt elimination was successful when performed in toluene as solvent. For compounds 2-6 the single-crystal X-ray structures were determined. Variable-temperature NMR spectra are reported for 2, 3, and 5.