Bismuth allyloxides, [Bt(OR)(3)] with R = CH2CH=CH2, CH(CH3)CH=CH2, C(CH3)(2)CH=CH2, and CH2CH-C(CH3)(2), can be prepared by alcoholysis of [Bi(O'Bu)(3)] and, in some cases, also via salt metathesis reactions starting from BiCl3 and sodium allylates They are readily soluble in common organic solvents, and NMR spectroscopic investigations do not provide any hint to aggregated species or any equilibria in solution. The majority of the compounds also proved volatile enough to be purified by sublimation Crystal structure analyses, however, provided evidence for a high degree of aggregation in the solid state, which leads to large rings and chains as structural motifs.