Alkynes occupy a prominent role as a coupling partner in the transition metal-catalysed directed C–H activation reactions. Due to low steric requirements and linear geometry, alkynes can effectively coordinate with metal d-orbitals. This makes alkynes one of the most successful coupling partners in terms of the number of useful transformations. Remarkably, by changing the reaction conditions and transition-metals from 5d to 3d, the pattern of reactivity of alkynes also changes. Due to the varied reactivity of alkynes, such as alkenylation, annulation, alkylation, and alkynylation, they have been extensively used for the synthesis of valuable organic molecules. Despite enormous explorations with alkynes, there are still a lot more possible ways by which they can be made to react with M–C bonds generated through C–H activation. Practically there is no limit for the creative use of this approach. In particular with the development of new high and low valent first-row metal catalysts, there is plenty of scope for this chemistry to evolve as one of the most explored areas of research in the coming years. Therefore, a highlight article about alkynes is both timely and useful for synthetic chemists working in this area. Herein, we have highlighted the diverse reactivity of alkynes with various transition metals (Ir, Rh, Ru, Pd, Mn, Fe, Co, Ni, Cu) and their applications, along with some of our thoughts on future prospects.