The chapter discusses the merit of metallacrown complexes to achieve multifunctional and multidimensional molecular materials. It introduces basic design strategies for discrete metallacrown complexes and discusses the predictability of molecular properties. Thereafter, it reviews two of the most outstanding molecular properties of metallacrown complexes, namely, the magnetic and luminescence characteristics. Most interestingly, for metallacrown complexes, such properties could be combined in one single molecule, giving rise to stable “multifunctional” molecular materials. Moreover, MCs are suitable building blocks to construct multidimensional coordination polymers. The chapter presents various possibilities to connect MCs leading to dimers of MCs over bigger compartments and triple-decker structures up to molecular chains, layers, and 3D frameworks. Finally, it will be shown that the properties of the single metallacrown motif allow for a predictability and rationalization of the materials properties.