The development of new sorptive materials with improved properties over the existing ones is one of the main research fields in the microextraction context. Polymers, which have demonstrated a great potential for extraction purposes, are excellent candidates according to their versatility, stability and efficiency. The versatility of polymers can be seen from two different perspectives: (i) they may develop different interaction chemistries with targets even allowing the ad-hoc selection of the polymer and (ii) they can be obtained in different formats (like fibers, coatings, membranes or beads). Polymeric nanofibers, especially those obtained by electrospinning, are characterized by large surface to volume ratio which enhances the extraction kinetics and capacity. In this article, the potential of nanofibers as sorptive phase is presented and discussed with selected references. In addition, the impact of nanofibers composites (either formed by combination of different polymers or combining polymers and nanomaterials) in microextraction is therefore considered. (C) 2016 Elsevier B.V. All rights reserved.