A series of fluorinated dendritic chiral ligands have been designed and synthesized. These fluorinated dendrimers are capable of forming a well-defined semi-rigid structure, which was revealed to play a vital role in the ruthenium(II) bifunctional catalyst for asymmetric transfer hydrogenation of prochiral ketone substrates. In contrast to the classical non-fluorinated dendrimer carrier, both NMR and DFT study exhibit that the introduction of fluorine atoms leads to considerable intramolecular weak interactions such as pi-pi stacking and hydrogen bonding interactions, which make the dendritic backbone exist with a semi-rigid structure in the catalyst. This influences the performance of the catalytic center in terms of the stability and reusability. This concept was employed as a strategy to design a new Ru(II)complex catalyst Ru-G-2 '-F, which demonstrated obviously improved recycling ability up to fifteen times. Significantly enhanced activity, high enantioselectivity and outstanding recycling ability have also been achieved even at high reaction temperature with Ru-G-2-F. (C) 2014 Elsevier B.V. All rights reserved.