Abstract The article discusses theoretical and experimental aspects of fabricating devices and developing methods for electrospun nanofiber-based solid-phase extraction (SPE). It seeks to encourage a better understanding of the use of electrospun nanofibers as a chromatographic sorbent bed. We base the discussion on fabricating six electrospun nanofiber-based SPE devices and evaluating their performance. We also categorize electrospun polymer nanofibers that are applicable as SPE sorbents as polystyrene type (relatively low mechanical strength) and nylon type (relatively high mechanical strength). We propose that the formats and the configurations of future electrospun nanofiber-based SPE devices may be guided by the mechanical strength of the polymer.