The Rh(III)‐catalyzed allylic C–H alkynylation of non‐activated terminal alkenes leads to linear 1,4‐enynes at room‐temperature. The catalytic system tolerates a wide range of functional groups without competing functionalization at other positions. Similarly, the vinylic C–H alkynylation of α,β‐ and β,γ‐ unsaturated amides gives conjugated Z‐1,3‐enynes and E‐enediynes.