Résumé : High selectivity is crucial for the functionalization of macrocyclic platforms bearing multiple identical functions. In the case of calix[6]arenes, only a few examples of efficient homo-functionalization have been reported. Herein, we describe the one-step synthesis of a tri-differentiated calix[6]arene and its use as a key intermediate to selectively access various homo- and hetero-functionalization patterns. In combination with the ‘all-but-one’ carbamatation methodology, this unique building block gives access to sophisticated calix[6]arenes that, until now, were inaccessible.