Cyclodextrin poly-functionalization has fueled progress in their use in multiple applications such as enzyme mimicry, but also in the polymer sciences, luminescence, as sensors or for biomedical applications… However, the regioselective access to a given pattern of functions on b-cyclodextrin is still very limited. Here, we uncover a new orienting group, the thioacetate, expanding the toolbox available for cyclodextrin poly-hetero-functionalization using DIBAL-H promoted debenzylation. The usefulness of this group is illustrated in the first synthesis of a precisely hepta-hetero-functionalized b-cyclodextrin. By way of comparison, a random hepta-functionalization would give 117655 different molecules. This synthesis is not simply the vain quest for the Holy Grail of CD hetero-functionalization, but it illustrates the versatility of the DIBAL-H oriented hetero-functionalization strategy opening the way to a multitude of useful functionalization patterns for new practical applications.