Molecularly imprinted polyethersulfone (PES) nano-scale fibers were prepared by using electrospinning technique, and then used for the recognition and binding of endocrine disrupter bisphenol A (BPA) from aqueous solutions. As an alternative to synthesizing molecularly imprinted nanofibers using `template-guided' or molecular self-assembly method, the route has proven to be one of simplicity and convenience. The imprinted PES nano-scale fibers with the diameter ranged from 200 nm to 500 nm could be easily used for the binding and recognition of BPA as that by using PES microfibers and particles, and the nano-scale fibers showed good performance for specific recognition of BPA. Significantly higher binding amount and speed were observed compared to the imprinted PES particles and microfibers.