Starting from a chiral building block--α-cyclodextrin--and rubidium salts, the crystallization of a complex of chiral helices, which constitute a "green" porous coordination polymer, has been realized. Cyclodextrin molecules coordinated by rubidium ions form porous, infinitely long left-handed helical channels, interdigitated with each other. A theoretical examination of the potential of this new material to act as a medium for chiral separation is presented.