Collagen is an excellent biomedical material with biocompatibility and biodegradability. However, the poor stability and low mechanical strength of collagen limit its application. Polyvinyl alcohol has good physical and chemical properties which can form a good bio-scaffold material by chemically coupling with collagen. Bioartificial liver (BAL) support has been researched and widely used in providing a bridge to patients waiting for a liver transplant or promoting liver regeneration, which can prevent complications caused by liver failure and improve survival rate. The scaffolds of BAL are important for the reproduction and biological function of liver cells. Polyvinyl alcohol (PVA) and collagen (COL) composite scaffolds was prepared in this work. PVA was modified by the amino silane and collagen crosslinked by glutaraldehyde. Then the heterogeneous mixture was treated by lysine and freeze-dried to obtain the PVA/COL composite scaffolds. The physical and chemical properties of the scaffolds were analyzed by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR). The biological properties of the scaffolds were evaluated by laser confocal, scanning electron microscopy (SEM) and CCK-8 experiments. FT-IR and XPS experiments demonstrated that collagen was successfully coupled to the PVA sponge and maintained a good triple helix structure. The results showed that the pore diameter of PVA modified by COL had uniform pore distribution with porosity of 21.33% and pore diameter of 168.68 μm. The contact angle of the scaffold material was 20.03°. The biological evaluation of scaffold materials showed that C3A cells adhered well on the PVA/COL scaffold and the proliferation test showed that the cells grew well on the composites. The proliferation of cells on the composite scaffolds was significantly different from the control group (P?0.01). The scaffolds prepared by the combination of PVA and COL had a promising application with the good physical and chemical properties.