Nanofibers have been considered as a potential kind of sorbent for solid phase extraction, accordingly nanofiber. based solid phase extraction (Nanofibers based solid phase extraction, NFs-SPE) becomes a popular research point of sample pretreatment technique. This article reviewed in and abroad research status of practical application in food, environmental and biological sample preparation based on nanofibers mat, and proposed that there was a dual "structure" -"activity" relationship between target adsorption efficiency and the two structures (nanometer morphological structure and molecular structure) of nanofibers, which would be the key breakthrough to explore adsorption mechanism.