Since various helical supramolecular polymers became available, their application to molecular chirality recognition have been anticipated but not extensively studied. So far, only a few examples of chiral reactions have been reported, but none for chiral separation. Here, we report the application of a helical supramolecular polymer to the enantio-separation of chiral guest molecules. The monomer of this supramolecular polymer is the salt-pair of a dendritic carboxylic acid with an enantiopure amino alcohol. In an apolar solvent, this salt-pair stacks via hydrogen bonds to form a helical polymer. In conjunction with this carboxylic acid, various amino alcohols afford supramolecular polymers, whose helical handedness is determined by the stereochemistry of the amino alcohols. When two salts with the same chirality are mixed, they undergo copolymerization, while those with opposite chirality do not. Owing to this stereoselective copolymerizability, the helical supramolecular polymer could bias the enantiomeric composition of chiral amino alcohols.