Abstract(S)‐4,4,4‐Trifluoro‐3‐hydroxybutanoic acid was used as a starting material for the synthesis of dendritic branches (16–21,30–32) which were attached to a chiral triol (6orent‐6), derived from (R)‐3‐hydroxybutanoic acid, to give CF3‐substituted dendrimers (33–36,38–40) and dendritic compounds (37) of 1st and 2nd generation. The key steps in these syntheses are diastereoselective aldol additions of dioxanone enolates (building blocks and intermediates6–15,22,23, and25–28) andWilliamsonetherifications of benzylic‐branch bromides with triols (intermediates and products16–21,28, and30–40). The surfaces of the dendrimers are covered with MeO (33–35,38–40) or allyloxy groups (36and37). The new dendrimers are characterized by NMR and mass spectroscopy.19F‐NMR Signals of the CF3groups reveal constitutional heterotopicities caused by substituents which are separated from the F‐nuclei by up to 15 bonds (through a