The mechanisms of aminocarbonylations and alkoxycarbonylations in coupling of aminophenols with iodoarenes catalyzed by the bidentate phosphorus ligand Pd complexes were explored with theoretical calculations. The origins of chemoselective carbonylation mediated by ligands and bases were disclosed. According to our calculations, the bifurcation points of reaction pathways caused by different ligands and bases combinations are (L1/L2)Int5, a [DPPP/DIBPP]benzoylpalladium(II)iodide complex. The affinity of (L1/L2)Int5 and adducts (K(2)CO(3 )and DBU), as well as the substrate itself, are the predominant factors of switching from aminocarbonylation to alkoxycarbonylation. The results reveal that K2CO3 directly exchanges iodine with (L1)Int5 and assists in hydrogen transfer in the DPPP-K2CO3 combination, in which alkoxycarbonylation is more favorable than aminocarbonylation, while for the DIBPP-DBU combination, iodine exchange is achieved by means of the hydrogen bond formed between the carbonyl group on (L2)Int5 and the substrate amino H due to the influence of the ligand, and then iodine exchange occurs; subsequently DBU-assisted amino H transfers to complete the aminocarbonylation. The proton transfer is the step that determines the chemoselectivity in the DPPP-K2CO3 combination. The iodine exchange determines the chemoselectivity between aminocarbonylation and alkoxycarbonylation in the DIBPP-DBU one. These results would be helpful to deeply understand the roles of each component in a chemoselective reaction in a multicomponent complex system.