A series of chiral bifunctional phosphinothioureas were synthesized and applied to the enantioselective Moritax2013;Baylisx2013;Hillman reaction of aromatic aldehydes with acrylates. In the presence of 8 mol % of organocatalyst 2e, the Baylisx2013;Hillman adducts were obtained in good enantioselectivities and up to 96 % yield under mild reaction conditions.