Nano-size fibers from lignocellulosic biomass were successfully obtained by akali-treatment and electrospinning using ionic liquid. The effects of the lignin and the hemicelluloses content on the spinnability, the web morphology, the micro-structure and the thermal stability of the electrospun fibers were investigated. The lower lignin content resulted in better spinnability, fine and uniform fiber diameter, higher crystallinity and decrease of thermal stability. This study reveals the possibility of the utilization for the lignocellulosic biomass other than pulp or cotton.