We describe herein an organocatalytic enantioselective approach for the construction of axially chiral sulfone-containing styrenes. Various axially chiral sulfone-containing styrene compounds were prepared with excellent enantioselectivities (up to >99% ee) and almost complete E/Z selectivities (>99% E/Z). Furthermore, the axially chiral sulfone-containing styrenes could be easily converted into phosphonic acid and S/P ligands, which could be potentially used as organocatalysts or ligands in asymmetric catalysis.