The contact between the blood and the surface of medical materials causes a series of rejection reactions. In this process, the plasma protein is adsorbed to the surface of materials within seconds and binds to glycoprotein receptors on platelets, causing platelet activation, coagulation cascade, and complement activation to form thrombus, which greatly limits the application of medical materials. In our work, the surface of poly(4-methyl-1-pentene) hollow fiber membranes (PMP HFMs) was coated with a diamond-like carbon (DLC) film by the ion plating method. The blood compatibility of the DLC coating was evaluated by protein adsorption, platelet adhesion, clotting time, red blood cell (RBCs) hemolysis, dynamic coagulation, and extracorporeal blood circulation tests. Compared with the unmodified PMP membrane, the DLC film could effectively reduce protein adsorption and platelet adhesion and prolong the coagulation time. The DLC coating showed BSA adsorption of as low as 0.53 μg/cm2 as well as a long activated partial thromboplastin time (APTT) value of 71.84 s. Furthermore, the PMP membrane modified with the DLC coating was used for extracorporeal blood circulation without thrombosis forming within 28 days. The DLC coating is one of the most promising medical coatings as an artificial lung membrane in extracorporeal membrane oxygenation (ECMO) equipment.