Solidified the polyvinyl alcohol water solution with different ratio of kaolin to fabricate hemostatic membranes by electrospinning. The SEM and EDS images showed that kaolin had been distributed on the membranes’ fibers. The hemostatic performance experiments showed that membranes made from10% PVA (mass ratio)/2% kaolin (mass ratio) solution performed best on hemostatic quality. It coagulate pig blood in vitro by 254 ± 2 s, and the blood loss and clotting time on SD rats’ hepatic injury experimentwere 167 ± 9 s and 0.21 ± 0.05 g, respectively. The further study on the hemostatic mechanisms, PK2 showed that it could decrease 7.2% and 4.7% clotting time on the APTT (activated partial thromboplastin time) and PT (prothrombin time) tests comparing with the controls, respectively, and it formed strong blood clots about 8 minutes. Combining with the low cytotoxicity and low hemolysis ration, it could be concluded that the PVA/kaolin electrospun membranes had high prospect on commercial application.