Photocatalytic degradation is one of the most popular routes applied in the wastewater treatments. But the most used nanoparticle photocatalysts have a serious drawback that the particles are not easy to precipitate and recover from water, which seriously hinder its applications. In this study, titania/porous carbon fibers composite prepared by a simple self-template method with micro-meter long carbon fibers and titania nanoparticles as precursors was investigated to solve these issues. The obtained composite can precipitate from the solution easily, which is the major reason that it can be used in actual applications. We found that the titania particles, as catalysts, could enhance the reaction between carbon fibers and oxygen during the calcinations process, and as a template, would determine the size and position of the pores on the fibers surface simultaneously. Due to the unique porous structure, the titania/porous carbon fibers composite shows considerable adsorption and high photocatalytic activity. Combining the advantages of titania and carbon fibers, the composite can be also applied in many other fields, such as water splitting for hydrogen and lithium ion batteries.