The first direct alkynylation of 2-vinylphenols was developed. The rationally optimized hypervalent iodine reagent TIPS-EBX* in combination with [(Cp*RhCl₂)₂] as a CH-activating transition metal catalyst enables the construction of a variety of highly substituted 1,3-enynes in high yields of up to 98 %. This novel CH activation method shows excellent chemoselectivity and exclusive (Z)-stereoselectivity, and it is also remarkably mild and tolerates a variety of functional groups. Furthermore, synthetic modifications of the resulting 1,3-enynes were demonstrated. To our knowledge, this is the first example for an OH-directed CH alkynylation with hypervalent iodine reagents.