Microscale extraction has gained attention in sample preparation due to its features like high throughput analysis, low solvent and sample consumption, easy operation, eco-friendliness, automation and miniaturization. Sorbents of versatile natures have diversified the applications. A variety of extraction sorbents have been fabricated and used in microextraction with varying efficiency. Electrospinning has emerged as a unique method to fabricate nanofibers with high surface area and excellent thermal and mechanical stability. Various types of electrospun fibres with controlled morphology, diameter and compositions have been introduced as solid phase microextraction sorbents. In this review, the applications of electrospun fibres have been highlighted as microextraction sorbents in fields including environment, food, protein and metabolite analysis and drug monitoring. The electrospinning technology improves analytical performance of microextraction analysis. Factors contributing towards the efficiency of electrospun fibers in separation science have been encompassed. Key parameters like versatility and selectivity towards variety of samples using electrospun fibers in microextractions are explored.