The electrospun fibers were manufactured from multifunctional small molecules through in-situ photopolymerization during the electrospinning process. In this study, Tetrabutylammonium Bromide (TBAB) was added to enhance the conductivity of the solution in order to improve spinnability. The synchronous matching of photopolymerization and electrospinning was investigated by real-time Infrared Spectroscopy (RTIR). The surface morphology of fibers was studied by SEM, and the chemical structure of fibers was characterized by FTIR. The residual of photoinitiator was investigated using UV-vis absorption spectroscopy, and the solvent resistance of fibers was characterized by soaking in different solvents. It provides an approach to prepare electrospun fibers from small molecules without using any solvents or heat. (C) 2017 Elsevier B.V. All rights reserved.