Dendrigraft polysiloxanes bearing 3-chloropropyl functional groups pendant to the polymer branches of the last generation were synthesized by the graft on graft method. First, branched polysiloxanes of various topologies, star, comb, and dendritic functionalized with pendant vinyl groups, were prepared. Hydrosilylation by dimethylchlorosilane transformed these groups into silyl chloride functions. Living polysiloxanes obtained by the anionic ring-opening polymerization of 2,4,6-tri-3-chloropropyl-2,4,6-trimethylcyclotrisiloxane were terminated on these silyl chloride groups which resulted in the grafting of the 3-chloropropyl functionalized polysiloxane on the branched polysiloxane core. The 3-chloropropyl groups on the dendrigraft were further used for the quaternization of dimethyloctylamine, 2-hydroxyethyldimethylamine, and triethylamine producing quaternary ammonium salt (QAS) groups. Dendrigrafts having an ionic corona and relatively hydrophobic core were synthesized. Preliminary investigations of the behavior of these polymers in aqueous media indicated their strong tendency toward aggregation and the ability to drive solubilization of organic compounds.