Abstract The oxidation of methane, ethane, propane, and n -butane has been studied over CeO 2 and Samaria-doped ceria (SDC) catalysts. The rates for methane and ethane were found to be indistinguishable over the two catalysts, while the rates for propane and n -butane were much higher on ceria compared to SDC. The difference between n -butane oxidation over ceria and SDC is shown to result from a low-temperature rate process on ceria that is not present on SDC. Measurements using CD 4 and C 4 D 10 show that both low- and high-temperature rates exhibit a similar kinetic-isotope effect; however, the low-temperature process is half-order in O 2 , while the high-temperature process is zero-order. Pulse studies demonstrate that oxygen from the bulk becomes accessible for reaction at approximately the same temperature as that at which the high-temperature rate process becomes important. The implications of these results for understanding the effect of doping on reactions over ceria, and for characterization of oxides using standard test reactions, are discussed.