The bismuth carbamate Bi(O2CNPr2i)(3), a tetramer in the solid-state, has been synthesized and used to deposit mixtures of bismuth oxides by aerosol-assisted chemical oxide is a function of both temperature and run-time. Initially, delta-Bi2O3 is deposited, over which grows a thick layer of beta-Bi2O3 nanowires, the latter having an increasing degree of preferred orientation at higher deposition temperatures. The photocatalytic activity of a thin film of delta-Bi2O3 for the degradation of methylene blue dye was found to be similar to that of a commercial TiO2 film on glass, while the film overcoated with beta-Bi2O3 nanowires was less active. Exposure of Bi(O2CNPr2i)(3) to controlled, amounts of moist air affords the novel oxo-cluster Bi-8(O)(6)(O2CNPr2i)(12), whose structure has also been determined.