An enantiopure helical coordination polymer AgPF6·(R)-3 as crystalline solid was synthesized by the self-assembly of chiral binaphthyl-based ligand (R)-6,6′-di[6-(2,2′-bipyridyl)]-2,2′-diethoxyl-1,1′-binaphthalene [(R)-3] and Ag+ ion. The single crystal structural analysis indicates that this polymer exhibits an infinite cylindric single-stranded M-helical structure with local configuration at each tetrahedral metal center. However, the extended structure is dissociated into some oligomeric fragments in solution. The 1H NMR spectra of complex AgPF6·(R)-3 show that the ligand possesses a good C2 symmetry, and the chemical shifts of the protons depend on the concentration and temperature. In addition, there are rapid dynamic exchanges among some oligonuclear fragments in the solution of AgPF6·(R)-3.