Electrospinning of nanofibers of materials that are difficult to process using conventional techniques is reported. Two fluids are electrospun (see Figure) into fibers with core/shell morphology. The "electrospinnable" shell fluid serves as a process aid to electrospin the core fluid. Three examples are illustrated: production of fibers with diameters less than 100 nm, fibers formed of low-molecular-weight polyaniline and non-blended electrospun silk fibers.