A series of highly active MnO2@REOx (RE = Gd, Sm, Ce, and La) catalysts were successfully synthesized via in situ growth on the surface of MnO2, wherein the rare earth oxides were planted on the defect sites left by hydrogen peroxide etching of the surface of MnO2. Their physicochemical performance was investigated by scanning electron microscopy with energy-dispersive spectroscopy (SEM-EDS), X-ray diffraction (XRD), N2 adsorption-desorption, X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction with hydrogen (H2-TPR), and temperature-programmed desorption of oxygen (O2-TPD). The catalytic properties are compared through the catalytic oxidation of chlorobenzene. Among all catalysts, MnO2@GdOx showed better mobility of surface lattice oxygen and higher molar ratios of Mn4+/Mn3+ (1.10) and Oads/Olatt (0.45), which promoted the superior low-temperature catalytic activity for chlorobenzene oxidation. The long-term chlorobenzene oxidation test (18 h) at different temperatures and the experiments with a mixture of VOCs showed that the as-prepared catalyst not only possessed a high stability but also was suitable for the efficient and simultaneous removal of multicomponent VOCs (toluene, benzene, acetone, and chlorobenzene). This work also provided an idea for the further development of high-efficiency catalysts for the purification of VOCs from complex atmosphere environment.