Thermal stimulus has been considered as a promising strategy for controlling on-surface reactions, allowing the formation of diverse products on metal substrates. Here, we successfully achieve hierarchical dehydrogenation reactions of amino groups on a Cu(100) surface. By carefully adjusting the experimental parameters, we synthesize large-scale and low-defect density surface metal-organic frameworks on copper surfaces. Our work sheds light on a controllable route for the synthesis of high-quality metal-organic coordination supramolecular structures via on-surface chemistry.