Due to rapid industrialization and urbanization, addressing the pressing issue of environmental pollution, particularly indoor air quality, demands innovative solutions. Volatile organic compounds (VOCs), notably toluene, are prevalent indoor pollutants that necessitate effective adsorption and removal strategies due to their adverse health impacts. Here, we propose a novel method for crafting a multifunctional air-filter membrane capable of simultaneous toluene adsorption and photocatalytic degradation across diverse light conditions, thus facilitating the development of a reusable air filtration system. This study outlines the successful synthesis of an air filter membrane by illustrating the in-situ growth of MIL-100(Fe) particles on polyacrylonitrile (PAN) nanofibers loaded with TiO2 nanoparticles, resulting in the formation of a PTF membrane. The PTF membrane exhibits an exceptional toluene adsorption efficiency of 98 % and a high toluene capacity of 383.94 mg g−1 (4.166 mmol/g), with a corresponding partition coefficient (PC) of 38.39 L/g ± 1.41. Notably, its design enables functionality, demonstrating impressive photocatalytic degradation efficiencies of 62.3 %, 71.3 %, and 80.2 % under UV, visible, and combined UV–visible light, respectively. This high efficiency is attributed to the PTF membrane’s reduced bandgap and enhanced light-absorption capabilities. Under the combined light conditions, the PTF membrane achieved the highest space–time yield (STY) of 0.197 mol/g/h and the highest reaction kinetic rate for toluene degradation, determined to be 6.34 × 10-8, surpassing the performance observed under individual UV and visible light sources. Moreover, the regeneration cycle of the PTF membrane demonstrates minimal efficiency loss, ensuring prolonged performance. The developed PTF membranes demonstrate notable stability and resilience even under the most extreme humid conditions, suggesting their strong potential for future applications in air filtration. This innovative approach offers a straightforward and environmentally friendly method for fabricating metal–organic framework (MOF)-based photocatalytic filters tailored to indoor VOC purification systems. This study is expected to significantly advance efforts aimed at improving and managing air quality, thereby fostering a healthier and more sustainable environment.