The pursuit of high-performance non-precious metal catalysts for Volatile Organic Compounds (VOCs) abatement is paramount in meeting stringent environmental regulations. In this study, we present a groundbreaking approach by crafting a highly defective Co3O4 catalyst through a strategic process involving Mg doping and subsequent partial de-doping. The catalyst exhibited an exceptional activity in the oxidation of formaldehyde (HCHO), achieving a remarkable conversion rate of 2.92 μmol·m−2·h−1, which is 3.1 times that of the pristine Co3O4 at 100 °C and an HCHO space velocity of 75,000 mL·g−1·h−1. Our methodology involves a dual-action process of doping and de-doping, orchestrating the introduction of significant structural and surface defects. These include surface cracks, lattice distortions, cationic vacancies, oxygen vacancies, lower metal coordination, and more. This orchestrated creation of defects serves to amplify the generation of active oxygen sites, thereby enhancing the intrinsic oxidative ability of the catalyst. The net result is a lowered activation energy barrier for HCHO, further contributing to the catalyst performance enhancement. This study not only establishes a new benchmark for Co3O4 catalysis but also provides insightful paradigms for the role of defects engineering in promoting non-noble metal-catalyzed volatile organic compounds oxidation.