Bimetallic synergistic catalysis is one of the most effective and powerful strategies for the synthesis of oxazolones, an important species in organic synthesis. In this work, the mechanism of AuCl(PMe3)/AgOTf-Pd(0) ([Au-Pd]) bimetallic catalyst-catalyzed oxazolone synthesis using N-alkynyl carbamates as precursors was studied in detail by DFT calculations and the catalytic performances of a series of bimetallic catalysts were evaluated. The results show that the reaction begins from the [Au]-catalyzed cycloisomerization of N-alkynyl carbamates. After the five-membered intermediate is formed, the [Pd(0)]-catalyzed cycle starts, which contains three steps: oxidation addition, transmetalation, and reductive elimination. The whole reaction belongs to a catalyzed catalysis, and the reductive elimination is the rate-determining step. In the transmetalation process, both the [Pd(0)] catalyst and the ionic bridge are necessary. For the [Au-Pd]-catalyzed process, it is Cl- as the bridge, not OTf-. The cheaper metal compound, AgCl(PMe3), can serve as the alternative of AuCl(PMe3) to co-catalyze with the [Pd(0)] catalyst for the title reaction.