Titanium dioxide (TiO2) is one of the most common photocatalysts. In this study, TiO2-vermiculite composite nanofibers with a mesh structure and a diameter of approximately 300 nm were prepared via sol-gel approach combined with electrospinning technique. The samples were characterized by X-ray diffraction, scanning electron microscopy, ultraviolet-visible spectroscopy, etc. The photocatalytic property was also evaluated. The TiO2-vermiculite composite nanofibers annealed at 550 °C for 3 h exhibited the best absorption and photo-degradation ability for the treatment of methylene blue. The results implied that the combination of mineral vermiculite powders with TiO2 enhanced the absorption-degradation performance of the as-prepared photocatalytic materials, consequently promoting the materials' ability to degrade methylene blue.