Nanoscaled photocrosslinkable polystyrene methylene cinnamate (PSMC) nanofibers were fabricated by electrospinning. The PSMC was prepared by the modification of polystyrene as a starting material via a two-step reaction process, chloromethylation and esterification. The chemical structure of PSMC was confirmed by 1H NMR and Fourier transform infrared spectroscopy (FT-IR). The photosensitivity of the PSMC was investigated using ultraviolet (UV) spectroscopic methods. Electrospun PSMC nanofiber mat showed excellent solubility in many organic solvents. UV irradiation of the electrospun mats led to photodimerization to resist dissolving in organic solvents. The morphology of the nanofiber was observed by scanning electron microscopy (SEM) and the result indicated that the average diameter of nanofibers is 350 nm and the crosslinked nanofibers were not collapsed after dipping into organic solvent showing good solvent-stability. This photocrosslinked nanofibers has the potential application in filtration, catalyst carrier and protective coating.