Challenges associated with analyte and matrix complexities and the ever increasing pressure from all sectors of industry for alternative analytical devices, have necessitated the development and application of new materials in analytical chemistry. To date, nanomaterials have emerged as having excellent properties for analytical chemistry applications mainly due to their large surface area to volume ratio and the availability of a wide variety of chemical and morphological modification methods. Of the available nanofibrous material fabrication methods, electrospinning has emerged as the most versatile. It is the aim of this contribution to highlight some of the recent developments that harness the great potential shown by electrospun nanofibers for application in analytical chemistry. The review discusses the use of electrospun nanofibers as a platform for low resolution separation or as a chromatographic sorbent bed for high resolution separation. It concludes by discussing the applications of electrospun nanofibers in detection systems with a specific focus on the development of simple electrospun nanofiber based colorimetric probes. (C) 2011 Elsevier B.V. All rights reserved.