The first enantioselective synthesis of axially chiral styrene-type allylamines was achieved through chiral phosphoric acid mediated atroposelective reductive amination of 1-enal substituted 2-naphthols. This protocol features a broad substrate scope, good enantioselectivities (up to 90% ee) and mild reaction conditions, thus providing a new entry to the challenging atropisomeric acyclic styrene scaffolds.