Three tetraorganodistannoxanes containing silicon were synthesized and their catalytic properties in esterification and acetalization were observed via the reac-tions of acetic acid with isoamyl alcohol and butyralde-hyde with glycol. The factors affecting the reaction, such as the catalyst dosage, reaction time and solvent, etc. were discussed. The results show that the three tetraorganodis-tannoxanes displayed similar good catalytic activities compared to dichlorotetrabutyldistannoxane in esterifica-tion and acetalization. When the dosage of [ClBu2SnOSn-(CH2SiMe3)2Cl]2 was 1.5% based on the mass of reactant, the yield of isoamyl acetate was 91.8% and the yield of butyraldehyde glycol aceta194.2%. The different alkyl and bridging groups on Sn sites in the structure of tetraorga-nodistannoxanes showed some influence on the catalytic activities of these compounds.