Herein, we describe a Brønsted-acid-catalyzed enantioselective desymmetrization of 1,3-diols with alkynes through a hydroalkoxylation/hydrolysis process. The reaction leads to the atom-economical synthesis of valuable chiral β-amino alcohols under mild reaction conditions. Further synthetic transformations based on the β-amino alcohol moiety provide divergent approaches toward chiral N-containing heterocycles.