Superhydrophobic nanofiber films were created from electrospun nanofibers with undulated surfaces at multiple scales in micrometers and nanometers. The electrospun nanofibers were produced out of aqueous solutions which contained water-soluble polymers and different colloids: monodisperse silica or polystyrene microspheres for larger particles and monodisperse silica nanoparticles for smaller particles. Various types of fibrous films were produced depending on the properties of the dispersing medium, the effects of additives, and the compositions of the bidisperse colloids. When polystyrene microspheres were used as sacrificial templates, macropores were left behind in the nanofibers during the removal of polystyrene microspheres by calcination. The nonwoven films of electrospun nanofibers, which were decorated with silica microspheres or macropores, could be continuously produced with considerable ease under a relatively wide range of operating conditions. The surface properties of the films were characterized by contact angle measurement and an X-ray photoelectron spectrometer. Through the surface modification of the electrospun nanofibers with fluorinated silane coupling agents, superhydrophobic surfaces with low sliding angles were successfully prepared.