This feature article provides an overview of the preparation of functional nanofibers by combined electrospinning, controlled radical polymerization and 'Click Chemistry'. A combination of the powerful capability of controlled radical polymerization and 'Click Chemistry' for the synthesis of functional macromolecules and on surface modification as well as their wide applicability to electrospinning materials, functional nanofibers with a crosslinked structure, core-shell structures, and switchable surface properties etc. were prepared. In addition, the applications of the functional nanofibers in antibacterial fields and controlled release are also explored.