Nanofibers are ideally suited to form a scaffold where multi-functional components can be hierarchically organized. Development in electrospinning in terms of fiber construction and organization, materials selection and incorporation, and post-spinning modifications have pathed the way for future developments of advanced composite systems. A nanocomposite system with up to five distinct levels of organization can be constructed using electrospun fibers. At the first level is a composite nanofiber. The second level is a second layer of composite material coated over the core composite nanofiber. Surface modification of the nanofiber will give the third level. The fourth level of organization is by arranging the nanofibers to form an assembly. Finally at the last level, the nanofiber assembly can be encapsulated within a matrix or form a bulk structure of a pre-determined shape. Examples of how hierarchically organized multifunctional nanocomposite can be used in healthcare, environmental and defense and security is discussed. (C) 2009 Elsevier Ltd. All rights reserved.