Hydrolysis of dibenzyltin dichloride in ethanol has been found to give an unprecedented carbonate anion (CO3 2-)-bridged double-ladder organo oxotin cluster, [(R2SnO)3(R2SnOH)2- (CO3)]2 (1,R = C6H5CH2), with five tin atoms in each ladder. With the aim of obtaining organooxotin clusters with large cavities suitable for host-guest chemistry, we used 1,1’-ferrocenedicar- boxylic acid (H2La) and hexanedioic acid (H2Lb) to replace the carbonate anions (CO3 2-), and thereby clusters [(R2SnO)3(R2SnOH)2La]2 (2) and [(R2SnO)3(R2SnOH)2Lb]2 (3) were ob tained. When 1 was treated with benzo ic acid (HLc) in different stoichiometric ratios (1:4, 1:10), ladder cluster (R2SnO)3(R2SnOH)2(Lc)2 (4) and drum cluster [RSn(O)Lc]6 (5) were obtained. Through the hydrolysis of Cy2SnCl2 (Cy = C6H11) and (C6H5CH2)2SnCl2, two interesting ethanolate-modified clusters [Cy2(C2H5O)SnOSn(C2H5O) Cy2]2 (6) and [(R2SnO)3 (R2SnOH) (R2SnOC2H5)(CO3)]2 (7) were ob tained. All the tin atoms in these ladder clusters are five-coordinate surrounded by two alkyl groups and three O atoms, and have distorted trigonal bipyramidal coordination environments with two carbon atoms and one O atom in the equatorial positions and two O atoms in the axial positions. The structures of all these compounds have been established by single-crystal X- ray diffraction analyses.