In this study, porous micron‐sized fibers of polylactic acid (PLA) are fabricated via electrospinning of PLA‐dichloromethane (DCM)‐hexane systems with no post treatment involved. Several compositions from the liquid‐liquid phase separated region of the phase diagram of this ternary system are selected and their electrospinnability are investigated throughout their phase separation process before gelation. We show that under constant processing and ambient parameters, there is a phase separation shelf time for each composition wherein the viscoelasticity of the systems is optimum to produce long, uniform porous fibers. For the first time, we investigate the effect of aging time during phase separation on the morphology of the electrospun fibers using scanning electron microscopy (SEM). Based on our results, certain phase separated systems provide a range of viscosity allowing for the production of porous spherical micro beads or fibers via electrospraying and electrospinning, respectively. It is also shown that obtaining long, uniform fibers from electrospinning of highly phase separated systems, e.g., a gel, is not feasible due to the high degree of crystallinity of their polymer‐rich domains and the solid‐like yielding behavior. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44862.