A new method for synthesizing chiral 3,3'-bis(N,N-dialkylaminomethyl)-1,1'-bi-2-naphthols with high enantiomeric excess is described. The procedure consists of bis-lithiation of diprotected (S)- or (R)-1,1'-bis(2-naphthol) followed by treatment of the intermediate with methyleneiminium salts. Mild reaction conditions prevent racemization and provide 3,3'-bis(N,N-dialkylaminomethyl)-1,1'-bi-2-naphthols or 3-(N,N-dialkylaminomethyl)-1,1'-bi-2-naphthols with an enantiomeric excess >99%.