Supramolecular coordination compounds bear exceptional advantages over their organic counterparts. They are available in one‐pot reactions and in high yields and display physical properties that are generally inaccessible with organic species. Moreover, their weak, reversible, noncovalent bonding interactions facilitate error checking and self‐correction. This Review emphasizes the achievements in supramolecular coordination chemistry initiated by serendipity and their materialization based on rational design. The recognition of similarities in the synthesis of different supramolecular assemblies allows prediction of potential results in related cases. Supramolecular synthesis obeys guidelines comparable to the “lead sheet” used by small jazz ensembles for improvisation and therefore more often leads to unpredicted results. The combination of detailed symmetry considerations with the basic rules of coordination chemistry has only recently allowed for the design of rational strategies for the construction of a variety of nanosized systems with specified size and shape. Luck or ability? In the field of supramolecular coordination chemistry, impressive advances have been achieved by the augmentation of initial serendipitous discoveries with rational design. Detailed consideration of symmetry and of the basic principles of coordination chemistry have led to rational strategies for the construction of diverse nanostructures with specific form and size (for example, 1; Fe: white, tripodal benzene ligand: yellow).