Cyclodextrins associated to metal centers or cyclodextrin\textendash metal hybrids have been developed for a very long time mainly because this association was seen as potentially mimicking metallo-enzymes. To generate such mimics it is necessary to functionalize cyclodextrins with multiple functions; this chapter presents the most frequently used and recent poly-modifications. The chapter gives an overview of the different cyclodextrin-based metal complexes, where the metal is precisely placed with respect to the cavity. It focuses on polyfunctionalized cyclodextrins, first describing complexes using cyclodextrins as platforms, then those using the cavity as a receptor for the ligand of the metal, and finally those using cyclodextrin as a host for the metal. The chapter describes applications of such complexes to metallo-enzyme mimicry. One of the main methods used to characterize cyclodextrins is nuclear magnetic resonance (NMR). Other usual techniques like infrared spectroscopy and mass spectrometry are also frequently used to characterize cyclodextrins.