The reaction between iodoarenes and acetylenes mediated by palladium was studied, showing selectivity changes based on the nature of the substituent. A new, phosphine-, copper-, and amine-free methodology was developed, in which the synthesis of trianisylethylene from 4-iodoanisole and trimethylsilylacetylene was promoted presumably by an N-heterocyclic-carbene derived from an ionic liquid and a palladium salt, using ethanol as the hydrogen source.