Automotive three-way catalysts (TWC) were characterized using temperature-programmed reduction (TPR), x-ray diffraction (XRD), Raman spectroscopy, chemisorption measurements and laboratory activity measurements. Capabilities and limitations of these standard analytical techniques for the characterization of production-type automotive catalysts are pointed out. With the exception of chemisorption techniques, all appear to have general utility for analyzing exhaust catalysts. The techniques were used to show that the noble metals and ceria in fresh Pt/Rh and Pd/Rh catalysts are initially highly dispersed and contain a mixture of interacting and non-interacting species. Thermal aging of these catalysts (in the reactor or vehicle) caused both precious metal and ceria particles to sinter, thereby decreasing the interaction between the two.