In this report, a polystyrene-ionic liquid (PS-IL) composite nanofiber was successfully produced for the first time by an electrospinning method. The electrospun composite films were characterized by SEM, FTIR, cyclic voltammetry, water contact angle (WCA) measurement, and conductivity measurement. The dimension, morphology, conductivity, and hydrophobicity of electrospun PS-IL composite film can be effectively controlled by altering the experimental parameters for electrospinning, especially the content of IL in the original electrospinning solution. The electrospun PS-IL composite film displayed both superhydrophobicity and conductivity, which may be ascribed to the micro- and nanoscale hierarchical structures of the PS-IL composite film and the intrinsic hydrophobicity and conductivity of the IL (BMIPF6). Entrapment of IL within polymer by electrospinning provides a facile way to create IL-based nanofibers and composite film and may find wide potential applications in the fabrication of controllable and functional surface.