Optically active exo-exo-2,3-camphanediol (CPO) (3) was synthesized from (+)-camphor. Chiral polymers poly(CPO-co-TDI) (6) and poly(CPO-co-IPDI) (7) were synthesized by the step polymerization of chiral compound CPO (3) with toluene-2,4-diisocyanate (TDI) and isophorone diisocyanate (IPDI). To investigate the stereo structure of the chiral polymers, two kinds of model compounds, exo-exo-2,3-di[(phenylamido)oxy]camphane (4) and exo-exo-2,3-di [(propylamido)oxy]camphane (5), related to polymers (6) and (7) were synthesized. Chiroptical characteristics and stereo structures of the chiral polymers were investigated using a circular dichroic spectrometer. The results obtained in this investigation suggest that the chiral polymers (6) and (7) have no one-handed helix conformation. The optical resolution ability as chiral adsorbent for HPLC of the chiral polymers was investigated. It was found that chiral polymers (6) and (7) are effective for the optical resolution of some racemates.