Electrospinning allows the production of nanofibers with diameters down to the range of a few nanometers. Self‐assembly processes driven by the coulomb interactions between charged elements of the fluids to be spun and their interactions with the external electrical field control nanofiber formation. Electrospinning involves thus a sequence of complex physical instability processes such as bending instabilities and axisymmetric instabilities. These processes induce extremely high extensional deformations and strain rates during fiber formation. Electrospinning is used predominantly to produce fibers from natural and synthetic polymers, and it has recently been exploited toward the production of metal, ceramic, and glass nanofibers employing precursor routes. The nanofibers can be functionalized during electrospinning by the incorporation of pores and fractal surfaces, and by introducing functional elements such as catalysts, quantum dots, drugs, enzymes, or even bacteria. The production of individual fibers, random nonwovens, or orientationally highly ordered nonwovens has been demonstrated based on appropriate selections of electrode configurations, die geometries, die arrangements, and so on. Compound co‐electrospinning and precision‐deposition electrospinning have opened novel routes for advanced fiber and nonwoven architectures. Nanofiber systems offer novel opportunities for broad areas of application in material science and life science. Examples are functional nanofibers for optoelectronics, sensorics, catalysis, textiles, high efficiency filters, and fiber reinforcement, as well as tissue engineering, drug delivery, and wound healing.