The synthesis and full characterization (mp, NMR, UV/vis, FTIR, and elemental analysis) of 13 bismuth aryloxides are reported. We have prepared bismuth aryloxides with alkyl, aryl, and allylic substituents on the aryl rings. Eleven of these bismuth aryloxides have been characterized with single crystal X-ray diffraction methods. Bismuth-donor interactions (donor = aryl, methoxy) are observed in several cases. Three unexpected bismuth oxo aryloxides (6c, 9c, 11c) were also isolated. Complex C(77)H(102)Bi(4)Br(6)O(8) (6c) results from apparent C-H activation and Bi-C bond formation as a sideproduct in the synthesis of Bi(O-2,6-(i)Pr(2)-4-BrC(6)H(2))(3) (6). Cluster 9c has a Bi(32)O(56) core, and cluster C(90)H(90)Bi(4)Li(2)O(12) (11c) is the second lithium bismuth oxo cluster reported to date.