The efficiency of dicarbene palladium(II) complexes and of simple palladium(II) acetate as catalysts for alkyne hydroarylation under liquid-liquid biphasic conditions involving an ionic liquid as the catalyst-containing phase is investigated. The results obtained under these conditions, both in terms of activity and selectivity, are compared with those previously obtained under homogeneous conditions. The catalytic efficiency of the systems is found to be markedly dependent on the nature of the anion of the ionic liquid. Suitable anions are found to significantly improve the catalytic performance in comparison to homogeneous conditions. Preliminary investigations on the recyclability of the system as well as the on advantages of using an acidic ionic liquid are also carried out.