A novel branched amphiphilic macromolecule on the basis of a sensitive Si-O-C structure was synthesized through a one-pot procedure. The self-assembly behavior of the molecule was tunable in non-aqueous media and the aggregates exhibited water stability thanks to the formation of vesicles with multi chamber structures, which protected the Si-O-C bonds from hydrolysis. The relation between the chemical bond nature and the self-assembly morphology was highlighted. The prepared aggregates were pH and temperature responsive.