Among organoaluminum reagents, alkynylaluminum species exhibit peculiar physicochemical properties and reactivity. Depending on the nature of easily controlled parameters such as substituents on the aluminum center or additives and solvent, their Lewis acidity and nucleophilicity can be independently fine-tuned in a very precise manner. This chapter describes the preparation of alkynylaluminum compounds, their structure, and their reactivity in several synthetic transformations involving the transfer of their alkynyl group such as nucleophilic substitution reactions, additions to C\textendash X multiple bonds, epoxide and aziridine ring-opening reactions, reactions with oxonium and iminium species, metal-assisted cross-coupling reactions, as well as in rearrangements. The reactivity of the triple bond of these reagents is also presented.