This article provides an overview of the development of palladium-catalyzed coupling reactions and the effects of ligand properties on the chemoselectivity of aryl (pseudo)halides. The selectivity of coupling reactions can be significantly influenced by applying appropriate ligands. This review discusses the chemoselectivity of triaryl and trialkyl phosphines, Pd(I) dimers, Buchwald-type phosphines, bidentate phosphine ligands, CataCXium phosphine ligands, SelectPhos, YPhos, and N-heterocyclic carbene catalysts. In each section, the properties of specific catalysts are described along with the chemoselectivity of reactions applying these ligand systems. Successful sequential chemoselective coupling approaches are presented as examples to demonstrate the capacity of catalysts to regulate chemoselectivity in coupling reactions, with significant implications for synthesizing pharmaceuticals, materials, and other valuable compounds.