Polychloral was prepared in which the optical activity arose exclusively from macromolecular asymmetry (i.e., helical conformation). Strong chiral initiators used at 0.5 mol% concentration gave optically active polychloral. Maximum values of optical rotations for polychloral samples were obtained with the following initiators: lithium methyl (+)-hydroxidemandelate [α]D25= +3600°, lithium methyl (-)-hydroxide-mandelate [α]D25= -4670°. A technique was developed to measure reliably the optical rotation of polychloral samples in film form.