Bisphenol A (BPA)-imprinted polyethersulfone (PES) microfibers for the recognition of BPA were prepared by means of wet-spinning method based on the liquid-liquid phase separation technique. Two kinds of the BPA-imprinted microfibers were fabricated with the diameters of about 85 lm and 265 lm, respectively. Extraction of BPA from the microfibers was carried out by immersing the imprinted microfibers into ethanol. In the recognition experiments, the binding amounts were about 24.0, 43.0, and 70.0 lmol/g for the nonimprinted microfibers, whereas those were about 50.0, 87.0, 120.0 lmol/g for the imprinted PES microfibers with the diameter of about 85 lm in 100, 200, and 400 lM BPA solution, respectively. Both of the binding amounts and the adsorption rate for the imprinted microfibers with smaller diameter were higher than that for the microfibers with larger diameters. The selectivity results indicated that the BPA-imprinted microfibers showed higher recognition coefficient (a) for BPA than phenol.