Direct air capture (DAC) holds significant promise as a viable solution to achieve net-zero emissions. Moisture swing adsorption (MSA), which utilizes water vapor pressure change, offers an energy-efficient method for atmospheric CO2 removal among various carbon capture technologies. However, scaling MSA technology has been hindered by limited sorption kinetics and capacity, primarily attributed to low active content in implementable materials. To address this, we introduce a facile fabrication strategy for structured adsorption films with exceptionally high active content. By leveraging a unique fibrillation process enabled through trace additions of hydrophobic polytetrafluoroethylene, we produce self-supporting porous film featuring extraordinary active content (99 wt %) and an ultra-thin profile (0.05 mm). The material exhibits extraordinary adsorption capacity (1.79 mol/kg) and a rapid adsorption half-time of 3.5 min, representing state-of-the-art performance among MSA systems. Scale-up testing confirms high moisture swing capacity (0.98 mol/kg) and productivity (3.4 mol/kg/day). Global potential modeling further reveals significant application prospects in arid/semiarid regions, where the film offers notable economic advantages over conventional DAC materials. This work provides fundamental insights for designing next-generation high-performance atmospheric CO2 capture materials.