Electrospinning is one of the most basic techniques for the production of nanoscale fibers. Electrospun nanofibers have excellent properties including small diameter, high surface area to volume ratio and high porosity,thus making them excellent candidates for filtration, catalysis, sensors as well as in biomedical applications. Moreover, multifunctional nanocomposites can be obtained with different functions and elements being hierarchically incorporated into electrospun nanofibers, which will largely broaden their applications in water treatment, healthcare, defense and other technologies. Herein, some recent progress in preparation, structures and properties of hierarchically organized polymer nanocomposites based on electrospun nanofibers are briefly summarized and discussed along with their prospect in practical applications.