The arylation reaction of styrene was tested in the presence of different transition metal-based catalysts, mainly iron-based, given its low cost and its nonpolluting and nontoxic characteristics. The study of the effect of sonochemical activation on the evolution of the selectivity of the reaction is also proposed. Higher efficiency was observed for a very short period of time of just a few minutes. Furthermore, an improvement of the selectivity of the arylation of the external carbon of styrene was observed.