We performed a comprehensive analysis of intermolecular carbonyl-carbonyl interactions in transition-metal complexes. Those interactions can be classified in two main types depending on the organometallic or organic nature of the donor carbonyl: M-CO center dot center dot center dot CO and R-CO center dot center dot center dot CO, respectively. By means of a combined structural and computational study we unraveled their geometrical features and strength. Moreover, electronic structure, natural bond orbitals, energy decomposition analysis, and quantum theory of atoms in molecules calculations were performed to try to understand their nature. Remarkably, we discovered that these carbonyl-carbonyl contacts have several features of the n -> pi* interaction. The charge transfer from an oxygen lone pair to an empty antibonding 7c orbital of the acceptor carbonyl is also accompanied by an electrostatic O delta- center dot center dot center dot C delta+ interaction. To the best of our knowledge this is the first report of an intermolecular n ->pi* interaction in metal complexes. These results might be significant, for instance, for the catalytic activation of carbonyl containing small molecules with metal compounds or in the design of hybrid organic-inorganic materials, metal-organic frameworks, and other extended structures.