Electrospun porous nanofibers have large specific surface areas and abundant active centers, which can effectively improve the properties of nanofibers. In the field of photocatalysis, electrospun porous nanofibers can increase the contact area of loaded photocatalytic particles with light, shorten the electron transfer path, and improve photocatalytic activity. In this paper, the main pore-forming mechanisms of electrospun porous nanofiber are summarized as breath figures, phase separation (vapor-induced phase separation, non-solvent-induced phase separation, and thermally induced phase separation) and post-processing (selective removal). Then, the application of electrospun porous nanofiber loading photocatalytic particles in the degradation of pollutants (such as organic, inorganic, and bacteria) in water is introduced, and its future development prospected. Although porous structures are beneficial in improving the photocatalytic performance of nanofibers, they reduce their mechanical properties. Therefore, strategies for improving the mechanical properties of electrospun porous nanofibers are also briefly discussed.