Electrospinning has been recognized as a feasible process for fabrication of continuous fibers with diameters ranging from several micrometers down to a few nanometers. This article presents an overview of recent progress in functional polymeric nanofibers prepared by electrospinning. Except of functional nanofibers fabricated from electrospinning of functional polymers, nanofibers from a combined technology such as coaxial electrospinning, electrospinning with living radical polymerization, and electrospinning with surface modification, would also be introduced in this review. Furthermore, the functionality and application of nanofibers would also be highlighted.