Kenaf has been interested as a reinforcing filler to improve the mechanical properties of polymer. Fabrication of Kenaf nanofiber is intended to broaden its scope and applications. However, its fabrication into nanofibers by electrospinning is difficult due to solubility problem. To improve the solubility, Kenaf was modified with carboxymethylation, which is confirmed by FTIR. The resultant polymer can be dissolved in N-methyl morpholine-N-Oxide (NMMO)/water co-solvent. Electrospinning conditions were also optimized for fabrication of PVA/Kenaf CMC nanofibers and it is the first time to fabricate nanofiber form Kenaf. The samples were characterized by SEM, FTIR and optical microscopy analysis.