With the rapid growth of environmental awareness and the high demand for alternatives to non-renewable materials, the study on developing sustainable and environmentally friendly materials has attracted significantly. Among them, nanocellulose and nanocellulose-based composites have attracted enormous interest due to their unique properties such as renewability, biodegradability, biocompatibility, non-toxicity, and environmental friendliness. In this study, cellulose nanocrystal (CNC) was isolated from used office papers and blended topoly(ethylene oxide) (PEO) for fiber composite production by electrospinning. Besides, the electrospun PEO was also successfully fabricated for comparison. The solution compositions and process conditions as the applied voltage and distance between the tip and the collector on the morphology of electrospun fibers were fully investigated. As a result, the PEO fibers with the average diameter of 151 ± 25 nm and the CNC/PEO fibers with the average diameter of 142 ± 30 nm were uniformly obtained.