Stereospecific hydrohalogenation reactions of electron-deficient alkynes,i.e.,2-alkynoic acids,2-alkynoates,2-propynamides,2-propynenitrile,1-alkynyl phosphonates/phosphine oxides,1-alkynyl sulfoxides/triflones,and 1-alkynyl iodonium salts with lithium or sodium halides to afford Z-alkenyl derivatives and their applications in synthesis of important intermediates as well as natural products were reviewed.