A facile one-step access to a chiral at metal ruthenium phosphoramidite tri(N-pyrrolyl)phosphine (PPyrl 3 ) complex is reported. In a one-pot reaction with PPyrl 3 and a chiral phosphoramidite ligand (L), the known ruthenium indenyl complex [RuCl(Ind)(PPh 3 ) 2 ] (Ind=indenyl) was converted to the chiral at metal complex [RuCl(Ind)PPyrl 3 (L)] as an optically pure single diastereomer in 59% isolated yield. The new complex was characterized spectroscopically and by X-ray crystallography, revealing a profound impact of the PPyrl 3 ligand on the geometry of the novel ruthenium complex.