The application of composite materials as catalysts for the oxidation of CO and other toxic compounds is a promising approach for air purification. In this work, the composites comprising palladium and ceria components supported on multiwall carbon nanotubes, carbon nanofibers and Sibunit were studied in the reactions of CO and CH4oxidation. The instrumental methods showed that the defective sites of carbon nanomaterials (CNMs) successfully stabilize the deposited components in a highly-dispersed state: PdO and CeO2nanoparticles, subnanosized PdOxand PdxCe1−xO2−δclusters with an amorphous structure, as well as single Pd and Ce atoms, are formed. It was shown that the reactant activation process occurs on palladium species with the participation of oxygen from the ceria lattice. The presence of interblock contacts between PdO and CeO2nanoparticles has an important effect on oxygen transfer, which consequently affects the catalytic activity. The morphological features of the CNMs, as well as the defect structure, have a strong influence on the particle size and mutual stabilization of the deposited PdO and CeO2components. The optimal combination of highly dispersed PdOxand PdxCe1−xO2−δspecies, as well as PdO nanoparticles in the CNTs-based catalyst, makes it highly effective in both studied oxidation reactions.