Hexapodand 1, which contains six phosphoryl groups at the lower rim of the macrocycle, was synthesized by the reaction of calix[6]arene with diethylchlorophosphate and sodium hydride. The structure is confirmed by X-ray studies: C₆₆H₉₀O₂₄P₆, Pbca, a = 14.867 (4), b = 18.577 (4), c = 26.510(6), D_c = 1.265g/ cm³, Z = 4, and R = 0.063 for the 4600 observed reflections. The molecule 1 exists in a centrosymmetrical flattened 1,2,3-alternate conformation, in which diametrically opposed benzene rings are parallel. Four phosphoryl groups are oriented away from the cycle, two other groups are self-included in the macrocycle cavity.