Zwitterionic rhodium (Rh) complexes with tethered chiral amino and ether groups were synthesized by the reaction of [(C2H4)(2)RhCl](2) with the 2,5-norbornadiene tether, (CH2)(4)R [2: R = (R)-NHCH(CH3)Ph, 3: (R)-OCH(CH3)Ph], followed by exchange of Cl with BPh4. The resultant Rh complexes, 2 and 3, catalyzed the polymerization of 4-dodecyloxy-3,5-bis(hydroxymethyl)phenylacetylene (1) to afford polymers [poly(1)s] with number-average molecular weights of 16000 and 82000, respectively. The poly(1)s showed clear circular dichroism resulting from their polyacetylene backbones, which indicates the formation of predominantly one-handed helical structures.