The highly enantioselective alkynylation of isatins, catalyzedbyabifunctional guanidine/CuI catalyst under mild reaction conditions,isdescribed. The reaction is broad in scope with respect to alkyl/aryl-substituted terminal alkynes and substituted isatins,t hus affording bioactive propargylic alcohols in excellent yields and enantioselectivities. Figure 1. Structures of chiral guanidinesa nd amide.