A series of the new chiral BINOL-based phosphite P,N-hybrid ligands was prepared. The coordination behavior of all the ligands was studied and the neutral complexes [Rh(CO)Cl(P N)] were synthesized in order to characterize a degree of the electronic non-symmetry of donating centers. Also the neutral and cationic complexes cis-[PdCl 2 (η 2 -P N )], cis-[PdCl 2 (η 1 -P N ) 2 ], cis-[PdCl(η 2 -P N )(η 1 -P N )] + Cl - , [Pd(allyl)(η 2 -P N )] + X - (X - =Cl - , BF 4 - ) were obtained and characterized. The new P,N-hydrid ligands gave up to 81% ee in the enantioselective Pd-catalyzed alkylation of 3-penten-2-yl carbonate by dimethyl malonate and up to 60% ee in the Rh-catalyzed hydrosilylation of acetophenone and acetylferrocene by diphenylsilane.