Efficient personal protection has emerged as a crucial approach for reducing pulmonary injury induced by particulate matter (PM). However, current personal protective equipments usually lack essential biosafety concerns and fail to own adsorbing/antioxidant/antibacterial function together, making it a challenge to develop an integrated platform with the above characteristics. Herein, a facile oxygen‐free hydrothermal strategy is proposed to synthesize new copper‐based metal‐organic frameworks, Cu‐HHTPs, (HHTP: 2,3,6,7,10,11‐hexahydroxytriphenylene), with great adsorbing/antioxidant/antibacterial activity and high biosafety. The Cu‐HHTPs can serve as an efficient additive incorporated with various fabrics including cellulose acetate (CA) membrane to achieve novel fabric composites, such as CA@Cu‐HHTPs, with ideal scavenging outcome for the main components of PM. Evidenced by the animal experiments, CA@Cu‐HHTPs can highly mitigate PM‐induced adverse effects via adsorbing PM, scavenging ROS, and killing bacteria, leading to a significant reduction in lung permeability, inflammation and oxidative stress, and pulmonary infection. Last but not least, a two‐week exposure of CA@Cu‐HHTPs exhibits no obvious damage toward the animals by examining their long‐term toxicity. Collectively, this study not only highlights the potential of Cu‐HHTPs as attractive additives for the preparation of fabric composites, but also lays out a new concept toward the development of new‐generation multifunctional personal protective equipment against PM.