Cellulose-based fibers were prepared by electrospinning from cellulose dissolved in NaOH/urea in the presence of a small amount of polyol binders. The as-spun products were examined with SEM. Pure cellulose solution did not produce fibrous materials, because it often formed spherical nanoparticles with diameters ranging from 100 to 300 nm. However, bicomponent fibrous materials were obtained successfully from mixtures of cellulose and HMPEG or PVA by electrospinning. The cellulose/HMPEG electrospun fibers had average diameters of 400 nm. The content of NaOH and urea as well as the stiffness of cellulose chains were found to have significant effect on the electrospinning process.