In this article, controllable micro/nanostructures were successfully obtained by electrospinning with the emulsion dispersions of polystyrene and poly(vinyl alcohol) (PS/PVA). The micro/nanostructure of electrospun PS/PVA emulsion dispersions such as corn-like, spindle-like, and bowl-like (or bracelet-like) were precisely controlled by regulating the electrospun parameters including the surfactant, the applied voltages, and the compositions of PS/PVA emulsion dispersions. The non-ionic surfactant (Poloxamer) was crucial for the stability of the PS/PVA emulsion dispersions although the surfactant in PS/PVA emulsion was in tiny amount. The high applied voltages were beneficial for the forming the lined-fiber structure but not for spheroids structure (bracelet-like structure). Moreover, the increasing content of PS in PS/PVA emulsion resulted in more spheroid structure than the lined-fiber. This work was meaningful for the forming mechanism of micro/nanostructure in emulsion electrospinning and made a potential contribution for controllable fabrication of micro/nanostructure of the electrospun PS/PVA emulsion dispersions. (c) 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46288.