A new strategy for a direct α,β,γ-functionalization of the γ-lactone framework in the corresponding 5-alkylidenefuran-2(5 H)-ones is reported. The developed approach is based on a stereocontrolled cascade reaction with 2-mercaptocarbonyl compounds proceeding in a sequence of thia-Michael/aldol/oxa-Michael reactions. Such a synthetic strategy allows for a construction of a unique polycyclic architecture containing γ-lactone, tetrahydrofuran, and tetrahydrothiophene ring systems. Excellent enantioselectivities and diastereoselectivities have been obtained in the presence of bifunctional catalyst derived from cinchona alkaloids.