Residual ethanol was used as an activation agent to control the status of corn cellulose (CN cellulose) solution and thereby the morphology of CN cellulose fibers after electrospinning. A suitable amount of ethanol could combine with the CN cellulose chains to reduce their ionic absorbance, improving the migration ability of ions in the cellulose-N,N-dimethylacetamide (DMAc)/LiCl-ethanol system. As a result, the entanglement of the molecular chains of CN cellulose in solution was reduced. Excess ethanol reduced the migration ability of ions and enhanced the strong entanglement of CN cellulose in solution. By thus adjusting the status of the CN cellulose solution, the fiber morphology and diameter distribution after electrospinning could be controlled. Based on the experimental results, this approach represents an important and effective approach using ethanol as an activation and adjusting agent for CN cellulose to achieve formation of high-quality electrospun fibers