We have evaluated the catalytic properties of Au-based nanostructures (including nanocages, nanoboxes, and solid nanoparticles) using a model reaction based on the reduction of p-nitrophenol by NaBH(4). From the average reaction rate constants at three different temperatures, we determined the activation energy, the entropy of activation, and the pre-exponential factor for each type of Au nanostructure. The kinetic data indicate that the Au-based nanocages are catalytically more active than both the nanoboxes and nanoparticles probably due to their extremely thin but electrically continuous walls, the high content of Au, and the accessibility of both inner and outer surfaces through the pores in the walls. In addition, a compensation effect was observed in this Au-based catalytic system, which can be primarily interpreted by a model based on kinetic regime switching.