The Kagome–honeycomb lattice has attracted significant interest as a platform for realizing exotic quantum states, owing to its unique electronic and magnetic properties. In this study, we report the synthesis of a two-dimensional Kagome–honeycomb lattice composed of nitrogen-doped macrocyclic aromatic hydrocarbons. By leveraging the synergistic influence of thermodynamically driven macrocyclization, the efficient organometallic template, and the steric hindrance induced by close-packed assemblies, submicron-scale Kagome–honeycomb crystalline films were obtained. With the combination of scanning tunneling microscopy (STM), high-resolution synchrotron radiation photoemission spectroscopy (SRPES), and density functional theory (DFT) calculations, the underlying reaction mechanisms were systematically revealed by investigating the reaction intermediates and products during the formation of the Kagome–honeycomb lattice. This work provides a promising pathway for the synthesis of Kagome–honeycomb lattices and offers a platform for exploring their novel physical properties.