Low-coordination Au sites have been proved to play a key role in defining the catalytic activity of Au nanoclusters (NCs). At the present time, it is still of great interest and challenge to design and synthesize catalysts containing the desired amount of low-coordinated Au atoms by a simple, easy, and large-scale method. In this study, PVP-protected 'crown jewel'-structured Au/Pd (CJ-Au/Pd) catalyst containing an abundance of top Au atoms were prepared by redox replacement reaction between Pd NCs and Au3+ ions. The catalytic activity of the CJ-Au/Pd NCs for aerobic glucose oxidation is about 3 times higher than that of the Au/Pd alloy NCs prepared by alcohol reduction method, although all of these NCs possess almost the same particle size.