Useful intermediates: Addition of silyl‐substituted chloroalkynes to terminalalkynes, namely chloroalkynylation, proceeds under palladium catalysis to afford (Z)‐1‐chloro‐1,3‐enynes (see scheme). The carbon–chlorine bond of the adducts is easily convertible to a carbon–carbon bond by using palladium‐catalyzed cross‐coupling reactions to provide a variety of 1,3‐enynes.