(S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthalene was prepared in three steps. (S)-(-)-1,1'-binaphthyl-2,2'-diol was firstly protected by trifluoromethanesulfonic anhydride, then after cross coupling with diphenylphosphine oxide, the title compound was synthesized by reduced with trichlorosilane. Structure characterization of the intermediates was conducted by methods of 31PNMR、1HNMR and HRMS. The optimum reaction conditions were determined as follows: n (Ⅱ) : n (Ph2PH=O) : n (DABCO) : n (Ni(dppe)Cl2) : n (HSiCl3) = 1 : 2.1 : 2.5 : 0.1 : 3. In the coupling step, the reaction temperature and time was 100 ℃ and 48 h, respectively. After reduced by trichlorosilane under reflux condition for 5 h, (S)-BINAP was got with the yield of 82.3% and 99.3% e.e..