Lignin is an abundant natural polymer in the biosphere and second only to cellulose; however, it is under-utilized and considered a waste. In this study, lignin was fabricated into nanofibers via electrospinning. The critical parameters that affected the electrospinnability and morphology of the resulting fibers were examined with the aim to utilize lignin as a resource for a new textile material. Poly(vinyl alcohol) (PVA) was added as a carrier polymer to facilitate the fiber formation of lignin, and the electrospun fibers were deposited on polyester (PET) nonwoven substrate. Eleven lignin/PVA hybrid solutions with a different lignin to PVA mass ratio were prepared and then electrospun to find an optimum concentration. Lignin nano-fibers were electrospun under a variety of conditions such as various feed rates, needle gauges, electric voltage, and tip-to-collector distances in order to find an optimum spinning condition. We found that the optimum concentration for electrospinning was a 5wt% PVA precursor solution upon the addition of lignin with the mass ratio of PVA:lignin=1:5.6. The viscosity of the lignin/PVA hybrid solution was determined as an important parameter that affected the electrospinning process; in addition, the interrelation between the viscosity of hybrid solution and the electrospinnability was examined. The solution viscosity increased with lignin loading, but exhibited a shear thinning behavior beyond a certain concentration that resulted in needle clogging. A steep increase in viscosity was also noted when the electrospun system started to form fibers. Consequently, the viscosity range to produce bead-free lignin nanofibers was revealed. The energy dispersive X-ray analysis confirmed that lignin remained after being transformed into nanofibers. The results indicate the possibility of developing a new fiber material that utilizes biomass with resulting fibers that can be applied to various applications such as filtration to wound dressing.