As an efficient hemostatic material for non-compressible bleeding, the abilities of forming strong physical barrier and effectively activating coagulation system is essential. In this study, an expandable polyvinyl alcohol/chitosan (PVA/CS) cryogel with good mechanical properties was prepared with green phase separation method. To enhance the blood cells adhesion and accelerate the production of blood coagulation factor, the quaternized chitosan-polydopamine (QCS-PDA) complex crosslinked with PVA/CS on the surface to obtain PVA/CS/QCS-PDA composite cryogel. The prepared cryogel showed obvious improved blood cell adhesion and clotting factors production compared with gauze and gelatin sponge. In addition, the introduction of QCS-PDA showed enhanced antimicrobial activity against S. aureus and E. coli. By adjusting the crosslinking of QCS-PDA, the QCS-PDA complex on the surface in response to external acid stimuli can be controlled to achieve rapid separation from wound. In the rat liver defect model and femoral artery non-compressible bleeding model, PVA/CS/QCS-PDA composite cryogel can quickly seal wounds and promote blood clotting. These results indicate that PVA/CS/QCS-PDA cryogel has great potential in non-compressible hemostasis.