A series of ferrocene-based bifunctional phosphinothiourea organocatalysts were synthesized and applied to the enantioselective Morita-Baylis-Hillman reaction of acrylates with nitrobenzaldehydes, giving the desired products in up to 99.7 % ee. The strong electron-withdrawing effect of nitro group and hydrogen bonding interactions between the thiourea moiety of catalyst and aldehyde might be crucial during the enantio-controlling process. [GRAPHICS]