Oxygen evolution reaction (OER) is of crucial importance to sustainable energy and environmental engineering, and layered double hydroxides (LDHs) are among the most active catalysts for OER in alkaline conditions, but the reaction mechanism for OER on LDHs remains controversial. Distinctive types of reaction mechanisms have been proposed for the O-O coupling in OER, yet they compose a coupled reaction network with competing kinetics dependent on applied potentials. Herein, we combine grand-canonical methods and micro-kinetic modeling to unravel that the nature of dominant mechanism for OER on LDHs transitions among distinctive types as a function of applied potential, and this arises from the interplay among applied potential and competing kinetics in the coupled reaction network. The theory-predicted overpotentials, Tafel slopes, and findings are in agreement with the observations of experiments including isotope labelling. Thus, we establish a computational methodology to identify and elucidate the potential-dependent mechanisms for electrochemical reactions.