Reaction of BiPh3 with salicylic acid (HO-2-C6H4CO2H, H2Sal) at room temperature in wet acetonitrile or nitromethane leads to the facile formation of an oxo cluster compound with formula [Bi4(m3-O)2(HSal)8] solvated by either MeCN and MeNO2 (1×2MeCN or 1×2MeNO2). This simple procedure affords a convenient, high yield (>80%) synthesis of a single bismuth oxo cluster. Both adducts exhibit a nearly planar Bi4(m3-O)2 core. The solvent ligands are situated in the same coordination sites in both but at long Bi---N and Bi---O distances. The ease of preparation as a pure compound makes this an ideal starting material for study of bismuth oxo-salicylate chemistry.