MOx/ABO3 is a promising catalyst for the high-efficiency removal of volatile organic compounds. However, this catalyst is limited on practical applications due to its complex synthesis procedure and high cost. In this work, the MnO2/LaMnO3 catalyst was prepared in situ using a facile one-step method for the first time, in which partial La cations were selectively removed from three dimensionally chain-like ordered macroporous (3DOM) LaMnO3 material. After selective removal, the obtained MnO2/LaMnO3 sample expressed an excellent catalytic performance on toluene oxidation. Toluene could be completely oxidized into CO2 and H2O at 290 °C over the MnO2/LaMnO3 catalyst with a toluene/oxygen molar ratio of 1/100 and a space velocity of 120 000 mL/(g h). In addition, the apparent activation energy value of MnO2/LaMnO3 was 57 kJ/mol, which was lower than those of other metal oxides catalysts. According to O2-TPD and XPS results, it is concluded that the high catalytic performance of MnO2/LaMnO3 was mainly associated with the large amount of oxygen species and the excellent lattice oxygen mobility. MnO2/LaMnO3 is a promising catalyst for the practical removal of volatile organic compounds due to its high efficiency, good stability, low cost, and convenient preparation.