Herein, we synthesized the well-defined catalysts of Mn-decorated single-crystal CeO2 nanorod (Mn/CeO2) with dominantly exposed {110} facets by incipient wetness impregnation method. Surface-modified Mn atoms can diffuse into the crystal lattice of CeO2-{110} facet to form Mn-O-Ce bond chains. The heteroatomic interfacial oxygen atoms in Mn-O-Ce bond chains as active oxygen species have a high-efficient performance, and resulting oxygen vacancy (Ov) sites can promote the adsorption and activation properties for O2. Mn/CeO2-10 catalyst exhibits superior catalytic activities and high stability. The related characterizations and DFT calculations results reveal that the Mn2+-Ov-Ce3+ active sites can decrease activation energy of O2 and desorption energy of NO2 in processes of NO oxidation to NO2, which is the crucial steps of NO2-assisted mechanism for soot oxidation. This work provides a new inspiration for rational modification of the near-surface atomic structure to obtain efficient catalysts for removal of soot or other pollutions.