In this study, woven fabrics with numerous electrostatic charges and desirable charge stability were investigated. A kind of core–shell monofilaments with different melting points between outer and inner layers were applied to wove the fabrics. These fabrics were hot coated through tourmaline particles as an charge enhancer at 122°C. Benefiting from the anions released by tourmaline particles and optimized content of the particles, the fabrics were endowed with surface potentials from −10 to −160 V and the voids content decreased from 45.4% to 41.2%, which contribute to the improvement in the filtration performance of the fabrics. A filtration mechanism was proposed while incremental surface charges with increasing tourmaline particles content have been confirmed through the noncontact measurement of electrostatic charges. The resultant fabrics exhibited a high filtration efficiency of 64.8% and superior long-term service performance. This study can provide a new application of the screen window for PM 2.5 governance.