AbstractThis study demonstrates the reaction behavior during the purification of model automotive exhaust gases over Pd catalysts before and after thermal degradation. In particular, to investigate the relationship between the Pd state and the reaction behavior of Pd/Al2O3 and Pd/CeO2−ZrO2 (CZ), operando X‐ray absorption spectroscopy measurements were performed during purifying exhaust gases over real and model catalysts mimicking the degradation of Pd particles and CZ supports after accelerated aging tests. The NO reduction activity of the aggregated Pd metal species was as high as that of the highly dispersed Pd species, but hydrocarbon (HC) poisoning was significantly enhanced by the aggregation of Pd metal particles caused by thermal aging. The existence of a three‐phase boundary (TPB) between the CZ, the Pd particles, and the gas phase strongly affected the catalytic activity at low temperatures, and the presence of a sufficient TPB facilitated the combustion of unburned HCs owing to the oxygen storage performance of CZ. Thus, the TPB reduced the poisoning of the precious metal surface by HC species at low temperatures. Therefore, the findings of this study will facilitate the development of next‐generation gas purification catalysts with high activity and durability.