We reported a mechanistic study on asymmetric O–H insertion reaction of α-diazoester with carboxylic acid using Rh2(OAc)4/chiral guanidine-amide as the cocatalyst by density functional theory B3LYP-D3­(BJ)/def2-TZVP//B3LYP-D3­(BJ)/6-31G**, SDD (SMD, Et2O). The catalytic reaction included two stages: (i) formation of Rh–carbene species, subsequently by the construction of C–O bond forming enol and (ii) chiral guanidinium salt-assisted H-transfer to the enol. In cooperative catalysis, Rh2(OAc)4 helped to form an enol intermediate via high-reactivity Rh–carbene species, while the in situ-formed guanidium carboxylate acted as a chiral proton shuttle to construct a hydrogen bonding net for the stereo-determinant protonation. The repulsions between the phenyl group of the enol intermediate and the cyclohexyl as well as the ortho-substituted isopropyl group of chiral guanidine played important roles in controlling stereoselectivity. A disadvantageous steric arrangement in si-face attack weakened the stabilizing electrostatic and orbital interaction of reacting species in the H-transfer step, enhancing the pathway to form a predominant product with R-configuration in the two competing pathways. A model was proposed to explain the asymmetric induction of chiral guanidine-amide in protonation.