N?Si doped carbon-embedded TiO2 composite fibers were prepared successfully by using centrifugal spinning and subsequent heat treatment with titanium tetrabutoxide, ethyl silicate, and Polyvinyl pyrrolidone as raw materials, as well propytrimethoxysilane (KH-560) as additives. The crystalline phase, morphologies, and groups of the prepared fibers were characterized by using X-ran diffraction, scanning electron microscopy, and Fourier transform infrared, respectively. The photocatalytic properties of the composite catalyst were investigated by using RhB as the oganic dye and ultraviolet as well visible light respective as irritator. The result indicated that Si and N atoms were doped into the lattice of TiO2. The average diameter, the surface morphologies, as well the photocatalytic activity of the fibers were controlled by the composition of raw materials, especially the concentration of KH-560. The photocatalytic performance of the novel TiO2 composite fibers reached their optimal in case the concentration of aminosilane coupling agents were 2.5 wt% and 3.75 wt% under ultraviolet and visible light irradiation, respectively.