The transition-metal-based heterogeneous catalysts for the decontamination of VOCs have emerged as a hot spot research trend over the past decades. However, their current catalytic performances are still limited, which are rooted in their low surface area and limited interfacial properties (e.g., surface oxygen species and oxygen vacancies). This study offers a facile synthetic method to prepare a unique hollow Cu 1.5 Mn 1.5 O 4 @Mndoped CuO nanocomposite catalyst. The resulting material consists of high surface area, abundant surface oxygen species, high bulk oxygen mobility, and rich surface oxygen vacancies. These features simultaneously contribute to promoting the catalytic complete oxidation of toluene. Thus, the Cu 1.5 Mn 1.5 O 4 @Mn-doped CuO nanocomposite exhibits superior catalytic activity, achieving a T 90 value of 274 °C at a GHSV of 96,000 mL•g −1 •h −1 , significantly outperforming the conventional Cu 1.