Iron-functionalized titanium dioxide (TiO2) composites with various Fe-to-Ti ratios were prepared on flexible glass fibers (GF-Fe-TiO2) via a sol-gel method, followed by a dip-coating process. The photocatalytic ability of these composites in degrading selected volatile organic compounds (VOCs; benzene, toluene, ethylbenzene, and o-xylene [BTEX]) at indoor concentration levels was examined. The GF-Fe-TiO2 composites were characterized using scanning electron microscopy, energy-dispersive X-ray elemental analysis, ultraviolet (UV)-visible spectroscopy, and X-ray diffraction. The GF-Fe-TiO2 composites showed superior photocatalytic performance to that of a reference glass fiber-supported TiO2 photocatalyst for the treatment of BTEX under visible light. However, this trend was reversed under UV irradiation. Specifically, the average BTEX photocatalytic efficiencies of the 0.01-GF-Fe-TiO2 composite in a 3-hr visible-light photocatalytic process were 4%, 33%, 51%, and 74%, respectively. Conversely, the average BTEX photocatalytic efficiencies obtained for GF-TiO2 were close to 0%, 5%, 16%, and 29%, respectively. These findings demonstrated that the GF-Fe-TiO2 composites could be applied to photocatalytically purify BTEX, especially under visible-light exposure. Moreover, the GF-Fe-TiO2 composites prepared with different Fe-to-Ti ratios displayed different BTEX photocatalytic decomposition efficiencies under visible or UV light, allowing for optimization of the Fe-to-Ti ratio (which was found to be 0.01).