Chiral Ag‐atropisomeric ligand species were studied in solution at different temperatures by 31P‐NMR spectroscopy. The analysis and understanding of key parameters in Ag‐BINAP complexes were considered in the context of an enantioselective transformation. An efficient silver‐catalyzed intramolecular [4+2] cycloaddition reaction of amide‐1,6‐enyne provided an enantiomerically enriched tricyclic compound using simple reagents and under mild reaction conditions.