Treatment of Bi(2)O(3) with the acids; S-(+)-10-camphorsulfonic, 2,4,6-mesitylenesulfonic and sulfamic, under sonication at room temperature in water for 2-4 h, results in the formation and subsequent crystallisation of polynuclear bismuth oxido-clusters; [Bi(18)O(12)(OH)(12)(O(3)S-Cam)(18)(H(2)O)(2)], [Bi(38)O(45)(O(3)S-Mes)(24)(H(2)O)(14)] and [Bi(6)O(4)(OH)(4)(O(3)SNH(2))(6)].