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Few synthetic methodologies that yield tris-functionalized C 3 v -symmetrical calix[6]arenes have been reported. In this work, three allyl protecting groups are selectively placed in 1,3,5 alternate positions of three pristine calix[6]arenes, each differing by their substituent on the large rim, resulting in three new C 3 v -symmetrical molecular platforms. Removal of the protecting allylic groups gives access to sophisticated calix[6]arenes that can be further modified. The potential of these new C 3 v -symmetrical molecular platforms is notably exemplified through the development of a new family of calix[6]arene-based N ligands.