ABSTRACTThe effects of polyethylene oxide (PEO) molecular weight (Mv), and volume fraction ( ) on the morphology of electrospun sulfur free softwood lignin nanofibers were investigated. Small amounts of PEO were used during preparations of the solutions to aid the electrospinning process. It was found that tripling the PEO volume fraction resulted in a transition from semi‐dilute un‐entangled to semi‐dilute entangled solutions. Conversely, the solution remained in the semi‐dilute un‐entangled regime as the molecular weight was increased by five times. The effects of molecular weight and volume fraction of PEO both on entanglement density and fiber morphology were unified by scaling PEO viscosities as a function of . We investigated and discussed conditions that would produce smooth fibers and conditions that would produce fibers with beads. In the case of beads‐on‐a‐string formation, bead widths remained constant regardless of the molecular weight and concentration of PEO, but the bead length changed. Additionally, we observed a decrease in the diameter of the fibers and the dimension of beads (length and width of beads) with an increase in the electric field used for electrospinning. The aspect ratio of beads increased with increases to both the electric field and the PEO molecular weight or concentration. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44172.