This tutorial review provides an introduction to the synthesis and characterization of chiral-at-metal complexes and their catalytic application in organic transformations. The synthetic access to these architectures either via chiral resolution or by employment of chiral ligands is described, characterization techniques for the complexes are referenced and the application of the R/S nomenclature is explained. Racemization and epimerization processes are often observed for the title compounds; the article gives mechanistic insights to these processes and describes how to recognize and document them. Finally, key catalytic applications in organic synthesis are presented and how the molecular architectures of the chiral-at-metal complexes lead to stereodifferentiation and, thus to enantiomeric excesses in the products.