Adsorption behaviors of metal porphyrins on graphene were studied by investigating adsorption kinetics, thermodynamics and density functional theoretical calculation. The interactions between poly aromatic nuclei structure of graphene and metal porphyrins were confirmed by XPS, TEM analysis and adsorption results, which account for adsorption of metal porphyrins. As the poly aromatic nuclei structure is the main structure of asphaltene, it also acted as active sites for adsorption of metal porphyrins. The differences of adsorption results between graphene and asphaltene indicated that the aliphatic side chains and other structures of asphaltene also have influence on adsorption process. Furthermore, chemical and physical adsorptions were also confirmed during the adsorption process of porphyrins on graphene.