Display omitted •Many Rh catalysts were tested for N2O decomposition under diesel conditions.•Rh/CeO2 is the only catalyst with good activity in a wet feed after aging.•Aging does not deactivate Rh/CeO2 but significantly increases its activity.•Removal O2 from the catalyst has been demonstrated to be the rate limiting step. Numerous Rh catalysts were evaluated for N2O decomposition for automotive applications. Some Rh-containing spinel materials exhibit excellent fresh activities in the absence of H2O but become inactive after hydrothermal aging or when tested in a wet feed. Rh catalysts supported on zeolites can be very active in a dry feed even after aging but are extremely sensitive to H2O. Rh/CeO2 is an exceptional catalyst for this reaction in the presence of both H2O and O2. Hydrothermal aging (750 °C/20 h) significantly increases its activity. A similar activity enhancement was found by calcining the support before Rh impregnation. XPS results show a surface enrichment of Rh species on the aged Rh/CeO2 catalyst relative to the fresh catalyst. Aberration corrected STEM images reveal that Rh is buried in the bulk on the fresh catalyst and pulled out onto the surface of the support after thermal treatments. All catalysts are inhibited by H2O with the zeolite-based Rh catalysts being the worst. The aged Rh/CeO2 catalyst is less sensitive to H2O relative to others. DRIFTS data show that H2O sensitivity is related to catalyst hydrophilicity; a high coverage of OH groups on a catalyst reduces its N2O decomposition activity. H2-TPR results show that a Rh/CeO2 catalyst can be readily reduced at < 100 °C. On a reduced Rh/CeO2 catalyst, near complete N2O conversion can be obtained with a lean feed at 250 °C for a duration equivalent to its oxygen storage capacity. The N2O-DRIFTS experiments over a pre-reduced Rh/CeO2 catalyst show that Ce3+ sites are quickly oxidized to Ce4+ upon contacting N2O at room temperature, resulting N2 and adsorbed O, with the latter being an efficient oxidizer. Based on these results, a N2O decomposition mechanism is proposed for the Rh/CeO2 catalyst.