(S)-3-Vinyl-2,2'-dihydroxy-1,1'-binaphthyl (2) was radically polymerized to obtain a polymer with excess of preferredhanded helical sense. The specific optical rotation [alpha](365)(25) of poly-2 was-1364.2 degrees and more than 4 times that of starting monomer 2. Poly-2 was confirmed to exist in the form of preferred-handed helical structure in solution by means of comparing the specific optical rotation, the circular dichroism (CD) and ultraviolet-visible (UV-vis) spectra with that of 2 and the model compound such as (S)-3-ethyl-2,2'-dihydroxy-1,1'-binaphthyl (3).