A chiral tetra-armed cyclen having four biphenyl groups, (S)-2 and (R)-2, were prepared. The Ag+-induced (HNMR)-H-1 and CD spectral changes of the new ligands showed that the conformation of the four biphenyl groups is controlled and the side-arms cover the Ag+ incorporated in the cyclen ring. Besides, drastic enhancements of CD intensities at a longer wavelength were observed. The exciton coupling of the CD spectra indicates that the side arms in (S)-2/Ag+ and (R)-2/Ag+ complexes are P-and M-forms, respectively.