Ordered imine phenanthroline Pd/Co self-assembled monolayers immobilized on graphene oxide (called as GO@Fmp-Pd(x)Cch(1-x)) designed was fabricated and characterized. Their catalytic properties were systematic investigated, in which the obtained [email protected] monolayer (TON = 46075, TOF = 23038 h(-1)) exhibited higher catalytic performance than that of monometallic counterparts for Suzuki-Miyaura coupling reaction with water as solvent due to the synergistic effects, the molar ratio and the physical chemistry properties of GO. Especially, distribution of active sites formed on the surface and inner of monolayer (denoted as 3D catalytic active centres called likely as MOFFs (Metallic OrganicFrame-Films)), in which relationship between actives and structure of the self-assembly monolayer played an important role on their catalytic activity. The oriental and special structure confirmed can be utilized not only help for easily insight into what happened during the catalytic process, supplying exposure more controllable active sites precisely in certain manner and stability by introducing different ligands and fabricating process. (C) 2019 Elsevier Inc. All rights reserved.