The experimental investigations on the catalyst [Cp*Rh(OAc) 2 and Cp*Ir (OAc) 2 )]-controlled [3 + 2] and [4 + 2] annulations of oximes with propargyl alcohols have been finished in our previous work and a supposed dual directing groupmediated reaction pathway has been deduced for the chemodivergent product synthesis. However, the detailed interaction modes of the dual directing groups binding with the corresponding metal center to achieve the above observed chemoselectivity remain unclear and even contradict. For instance, the calculational traditional dual direct coupling transition states suggested that both Cp*Rh(OAc) 2 -and Cp*Ir(OAc) 2 -catalyzed reactions would generate five-membered indenamines as the dominant products via [3 + 2] annulation. To address this concern, herein, systematic DFT calculations combined with proof-of-concept experiments have been carried out. Accordingly, a novel and more favorable M III -M V -M III reaction mechanism, which involves an unprecedented HOAc together with a hydroxyl group-assisted reaction pathway in which the hydroxyl group acts as double effectors for the formation of M−O coordination and [MeO•••H•••O(CCH 3 )O•••H•••O] bonding interactions, was deduced. Taken together, the present results would provide a rational basis for future development of the dual directing group-mediated C−H activation reactions.