The formation of solid solutions of cerium oxide with the oxides of calcium, manganese, or neodymium enhances the catalytic activity of cerium oxide for the total oxidation of methane, whereas solid solutions with lead oxide showed an opposite effect. Reasons for this are discussed in terms of oxygen vacancy concentrations and mobilities, local structure configurations, number of oxidation states of dopant, and electron transfer properties. The effects of increased oxygen ion mobility and a more beneficial local structure support the increased catalytic activity for the calcium- and neodymium-doped cerium oxide samples. In addition, a reduced energy for charge transfer from oxygen to cerium supports a higher activity for the calcium-doped sample. The activity data were fitted to an Arrhenius equation, and the apparent activation energies were found to be between 110 and 130 kJ/mol. The particle sizes and the BET areas of the samples were only little affected by the reactor runs, and none of the samples were subjected to phase changes.