The binaphtholic aldehydes dangled with dipicolyl amine moieties, (R)‐1, and (R)‐2, were synthesized. The reaction of (R)‐1 with an amino acid together with ZnII ion produces a monomeric complex that discriminates the chirality of the bound amino acid by 1H NMR. The same reaction of (R)‐2, which is different from (R)‐1 by only one nitrogen atom, generates a dimeric complex which is highly enantiospecific for the L‐form of amino acids such as Phe and Trp.