Abstract: Electrospun hierarchical porous materials with micro- and nanometer scale porous structure offer high specific surface area and unique properties for various applications. The preparation of electrospun hierarchical porous nanofiber mats is reviewed，including organic series and ceramic series. For the organic series，phase separation induced by solvent evaporation and other factors is the main mechanism of forming porous structure. While the template methods are often used to prepare inorganic porous nanofibers. The hierarchical pore structure further enlarges the surface area and enhances the hydrophobic property of the fiber mat，which alters the performance of the mat greatly.