Atmospheric ozone has long been a threat to human health, however, rational design of high-performance O₃-decomposition catalysts remains challenging. Herein, we demonstrate the great potential of a series of isomorphous bimetallic MOFs denoted as PCN-250(Fe₂M) (M = Co²⁺, Ni²⁺, Mn²⁺) in catalytic O₃ decomposition. Particularly, PCN-250(Fe₂Co) showed 100% O₃ removal efficiency for a continuous air flow containing 1 ppm O₃ over a wide humidity range (0 ‒ 80% RH) at room temperature. Mechanism studies suggested that the high catalytic performance originated from the introduction of open Co(II) sites as well as its porous structure. Additionally, at low pressures around 10 Pa, PCN-250(Fe₂Co) exhibited high adsorption capacities (89 ‒ 241 mg g⁻¹) for most VOCs, which are not only a class of hazardous air pollutants but also the precursor of O₃. This work opens up a new avenue to develop advanced air purification materials for O₃ and VOCs removal in one.