New chiral liquid-crystalline poly(vinylcyclopropane)s were prepared by free-radical ring-opening polymerization of the corresponding 2-vinylcyclopropane monomers. These side-group polymers had unconventional structures as they contained both linear and cyclic isomer repeat units. They formed an SmC phase around room temperature. General trends of the phase structures and transitions were found with the length of the spacer segment and the nature of the chiral substituent of the side-group mesogens.