: A method for the selective dimerization of styrenes and acrylates has been developed. The reaction is catalyzed by a very low amount of palladium acetate in molten tetrabutylammonium acetate without the need for any additional ligand. The use of this method enabled the coupling of substituted vinyl arenes in reasonable yields to give exclusively the (E,E)-1,4-diarylbutadiene motif within 7-10 h. Acrylates, on the other hand, exhibit higher reactivity, and the use of dibutyl acrylate resulted in the quantitative synthesis of dibutyl 2-methyleneglutarate in less than 2 h. This selectivity is unprecedented in the literature. The role of the ionic liquid and the different catalytic pathways involved in the two processes were also elucidated.