Effect of benzyl triethylammonium chloride (BTEAC) on the microstructure of electrospun bicomponent fibers, i.e., polyvinylidene fluoride (PVDF)/polycarbonate (PC), polyacrylonitrile (PAN)/polyethylene glycol (PEG), and PAN/PVDF, was investigated in this article. The evolution of morphology and microstructure of the above bicomponent fibers were examined by scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. The results showed that distinct core/shell structured fibers were successfully prepared from PVDF/PC and PAN/PVDF via introducing a small amount of BTEAC, whereas only cocontinuous structure was detected in the electrospun PAN/PEG fibers. This study could be an example of electrospun multipolymer dispersions influencing by an organic salt, and it could be extended to control the structure of carbon nanofibers via electrospinning. POLYM. ENG. SCI., 2012. (C) 2012 Society of Plastics Engineers