We successfully synthesized optically active polymers by using a chiral hisphosphine, (SS)-1,2-bis[boranato(t-butyl)methylphosphinolethane, as a key building block. Their structures were characterized with H-1, C-13, and P-31 NMR spectra. The obtained polymers exhibited different glass-transition temperatures depending on the structure of each comonomer, whereas a model compound had a melting point. According to circular dichroisin spectra, the difference in the stereochemistry of the comonomers yielded the different higher-ordered structures of the polymers induced by chiral phosphine units. (c) 2007 Wiley Periodicals, Inc.