Bisphosphine-catalyzed mixed double-Michael reactions have been developed to afford beta-amino carbonyl derivatives of oxazolidines, thiozolidines, and pyrrolidines in excellent yields and with high diastereoselectivities. Efficient reactions between amino-acid-derived pronucleophiles, such as beta-amino alcohols, beta-amino thiols, and gamma-amino diesters, as Michael donors and electron-deficient acetylenes, such as propiolates, acetylacetylene, and tosylacetylene, as Michael acceptors provided access to azolidines containing both diversity of substituents and asymmetry. This methodology-the first examples of mixed double-Michael reactions of acetylenesis operationally simple and involves mild conditions. Mechanistically, it constitutes a rare example of the anchimeric assistance of bisphosphines in organocatalysis.