A strategy to improve the toluene oxidation properties through La doping and citric acid modification is proposed. In particular, when the ratio of citric acid to metal is 2 (CCoLa-2), due to the differing nucleation rates of the La and Co precursors, the {1 1 0} crystalline facets in Co3O4 are exposed, which promotes the formation of more electron-deficient Co3+ ions along with an abundance of surface lattice oxygen, which facilitates the catalysis of toluene. Meanwhile, the interfacial effect produces by the doping of La induces the presence of La3+–O–Co3+/La3+–□–Co2+ structure in CCoLa-2, which reduces the electron concentration around the surface lattice oxygen and weakens the CoO bond intensity, thus enhancing the activity of the surface lattice oxygen. Finally, CCoLa-2 possesses outstanding oxygen replenishment ability to rapidly degrade the tough intermediate species benzyl alcohol and benzoic acid, thus accelerating the catalytic cycle.