We report the construction of complex metal‐organic assemblies at surfaces using concepts from coordination chemistry. Well‐ordered supramolecular assemblies and metal‐organic coordination networks with specific topologies and a high structural stability have been fabricated under ultra‐high vacuum conditions by sequential deposition of polyfunctional organic molecules and Fe atoms onto an atomically clean Cu(100) substrate. The structures were investigated at the molecular level byin‐situscanning tunneling microscopy. The precise control of the concentration ratio of the components and the annealing treatment allow for the assembly of distinct architectures. © 2003 American Institute of Physics