Nickel-and palladium-catalyzed cross-coupling reactions have attracted wide attentions, while ligand-controlled selectivity in these reactions are still elusive, and calculations can help obtain possible catalytic cycles to generate different products and provide insights into key factors of selectivity, which facilitates the development of new catalyst systems to control reaction selectivity. This review covers our efforts and some significant achievements from other groups on ligand-controlled reaction selectivity of coupling reactions, including introduction, computational methods, selectivity control by ligands in Ni-and Pd-catalyzed coupling reactions, as well as summary and future perspectives.