A highly efficient asymmetric synthesis of chiral thiochromanones is developed via Cu(I)/phosphoramidite catalyzed asymmetric alkynylation of thiochromones under mild reaction conditions. The catalyst system is tolerant of various thiochromone precursors and terminal alkynes. The established asymmetric transformation provides different enatiomeric-enriched thiochromanones with more molecular complexity and enables access to chiral thioflavanones, a subgroup of flavonoid by further functionalization.