Using polyvinyl alcohol (PVA) and nanocellulose (NC) as raw materials, PVA/NC nanofiber membranes were prepared by electrospinning. The hydrogen bonding, crystalline properties and microscopic appearance of PVA/NC membranes with different NC contents were characterized. The mechanical properties, liquid absorption and cytotoxicity of the nanofiber membrane were evaluated. The results show that the free hydroxyl group of the PVA/NC nanofiber membranes have a maximum value of 9% at a mass fraction of 6% NC. The crystallinity of the PVA/NC nanofiber membranes and the average diameter of the nanofibers decreased and then increased as the NC content increased, with a minimum value of 38.23% and 272.03 nm, respectively, at 6% NC content. At this time, the contact angle was the smallest. The maximum strength of the PVA/NC nanofiber membranes is 75.8% higher than that of the PVA membrane at 2% NC content. With increasing NC content, the absorption of water, PBS sustained-release suspensions and artificial blood by PVA/NC nanofiber membranes increases. Cytotoxicity tests have shown that PVA/NC nanofiber membranes are non-toxic, have good cytocompatibility and are expected to be used in the field of medical dressings.