The hydrolysis of [Bi6O4(OH)4(NO3)6]·H2O (1) in the presence of sodium alkylsulfonates gave the oxidobismuth sulfonates [{Bi38O45(C4H7SO3)8(NO3)14(dmso)19.5(H2O)2}][{Bi38O45(C4H7SO3)10(NO3)16(dmso)16(H2O)2}]·3H2O·3dmso (2, dmso = dimethyl sulfoxide), [Bi38O45(C6H13SO3)14(NO3)10(dmso)28] (3), and [Bi38O45(C8H17SO3)16(NO3)8(dmso)12] (4) upon crystallization from dmso. Compound 2 is the first example of a nanoscaled oxidobismuth cluster that is composed of both an anionic (charge 2–) and a cationic (charge 2+) fragment in the solid state. The clusters were characterized by elemental analysis, ESI mass spectrometry, IR and NMR spectroscopy, as well as thermal analysis. Crystals obtained for 2 were suitable for single-crystal structure analysis.