This paper reports a study of the formation of cellulose nanofibres from kenaf waste using chemical extraction method. The extracted holocellulose was then prepared for acid hydrolysis to form the cellulose. Before mixing it with polyvinyl chloride (PVA) solution and extruded using electrospinning under different parameters to produce PVA/kenafnanofibres. Results showed that the morphological structures of PVA/kenafnanofibres varied at different voltages. An increase in voltage from 10 kV to 20 kV produced more beads along the fibre length. In addition, the applied voltages were found to affect the resultant fibre diameter of the PVA/kenafnanofibres. The results also showed that the electrospinning parameters affect the shapes of the PVA/kenafnanofibre membranes. Based on the experimental works, the optimal applied voltage was found to be at 15 kV, where the resultant fibre diameter and membrane coverage area were approximately 43.9 ± 3.1 nm and 214.2 ± 15.8 cm², respectively.