In this study, the biocompatible copolymer Poly(lactic acid-co-caprolactone) (PLCL) doped with sulfonated gamma-Al2O3 nanoparticles was used for electrospun on stainless wires. The electrospun fibers were further sheathed by the self-polymerization of norepinephrine, a catecholamine found both in neuro-transmitters and mussel adhesive proteins, to improve the surface hydrophilicity and provide a smooth bio-interface. The modified electrospun fibers on stainless wires were developed as novel custom-made solid-phase microextraction (SPME) fibers. These fibers exhibited much higher extraction efficiency compared to the polydimethylsiloxane (PDMS) fibers, especially to the sulfonamides. The custom-made SPME fibers also showed excellent stability with the relative standard deviations (RSDs) of intra-fiber ranged from 1.98% to 9.86% and RSDs of inter-fiber ranged from 4.36% to 15.6%. Moreover, these fibers were also demonstrated to be anti-biofouling and suitable for in vivo sampling. The custom-made SPME fibers were successfully applied to determine the Pharmaceutical concentrations in living fishes and vegetables. The accuracies were verified by the comparison with liquid extraction and the sensitivities were demonstrated to be satisfying with the limits of detection (LODs) ranged from 0.16 ng/g to 5.35 ng/g in fish muscle and 0.02 ng/g to 8.02 ng/g in vegetable stem. (C) 2016 Elsevier B.V. All rights reserved.