In this study, porous ceramic fibers were prepared by the sol-gel-assisted electro-spinning process using colloidal dispersion of complex fluids for the application of phtotocatalysts. First, polystyrene nanospheres were synthesized by dispersion polymerization as sacrificial templates for porous fibers. Then, the mixture of polyvinylpyrrolidone and the ceramic precursor with the polymeric nanospheres was prepared as the spinning solution and self-organized by electro-spinning, followed by calcination of the electrospun composite fibers. The morphologies of the porous fibers could be controlled according to the size of the templates and the amount of the ceramic precursor. The nano-structure of the pores in the fibrous materials could also be adjusted as open or closed cavities with various potential applications. As a demonstrative application, the macroporous titania fibers could be utilized as photocatalysts for the removal of organic dyes dissolved in water. A better photocatalytic activity of the macroporous fibers with 700-nm pore diameter was observed compared to the result of nonporous titania fibers due to the increased porosity. Collectively, the macroporous ceramic fibers were found to be efficient functional materials to prepare the unique nano-structured materials other than simple nonporous fibers.