Graphene oxide (GO), reduced graphene oxide (rGO), and their derivatives are investigated for various biomedical applications explosively. However, the defective biocompatibility was also recognized, which restricted their potential applications as biomaterials. In this study, a facile biomimetic approach for preparation of biopolymer adhered GO (rGO) with controllable 2D morphology and excellent biocompatibility was proposed. Mussel-inspired adhesive molecule dopamine (DA) was grafted onto heparin backbone to obtain DA grafted heparin (DA-g-Hep) by carbodiimide chemistry method; then, DA-g-Hep was used to prepare heparin-adhered GO (Hep-a-GO) and heparin-adhered rGO (Hep-a-rGO). The obtained heparin-adhered GO (rGO) showed controllable 2D morphology, ultrastable property in aqueous solution, and high drug and dye loading capacity. Furthermore, the biocompatibility of the heparin-adhered GO (rGO) was investigated using human blood cells and human umbilical vein endothelial cells, which indicated that the as-prepared heparin-adhered GO (rGO) exhibited ultralow hemolysis ratio (lower than 1.2%) and high cell viability. Moreover, the highly anticoagulant bioactivity indicated that the adhered heparin could maintain its biological activity after immobilization onto the surface of GO (rGO). The excellent biocompatibility and high bioactivity of the heparin-adhered GO (rGO) might confer its great potentials for various biomedical applications.