The molecular composite composed of polyethylene (PE) and polyvinyl acetate) (PVAc) prepared using supercritical carbon dioxide (scCO2) and its surface modification for biocompatible surface demonstrated the creation of novel polymer biomaterials. In this study, this modification process was applied to the PE narrow tube (inside diameter: 300μm, outside diameter: 600μm, length: 5m) It was confirmed that PVAc was uniformly generated in PE tube by infrared imaging measurement of cross-section. After the acetyl group on the surface was hydrolyzed, phospholipid polymer was immobilized to the hydroxyl group on the surface of the tube. The phospholipid polymer immobilized surface showed a drastic reduction in protein adsorption. The surface of the minute and slender tube can be effectively modified using the feature of carbon dioxide whose surface tension is near zero. The modification technology by scCO2 is a promising for creation of variously-shaped new biomaterials.