The factors determining the catalytic performance of a recently discovered system for direct intermolecular alkyne hydroarylations, comprising a gold(I) complex of general formula LAuX (L = neutral ligand; X = weakly coordinating counteranion) and an ionic liquid as solvent, have been investigated. In particular, the effect of the ionic liquid anion, cation, and of the electronic and steric properties of the neutral ligand L have been considered. The results of the investigation shed some light in particular on the role of the anion, which is multiform and can potentially influence the catalytic performance in many respects, and on the role of the neutral ligand, which should be a relatively poor electron donor but not so much as to compromise the stability of the catalyst. Knowledge of the factors affecting catalytic performance will speed up the optimization of this catalytic system, in the case of direct alkyne hydroarylations with different substrates, and will also facilitate the extension of its application to other reactions.