We have carried out an X-ray structural study of the title complex (a CAD-4F diffractometer, λMoKα, graphite monochromator, ω/2Θ scan mode, θmax, direct methods, 1465 reflections, R=0.036). Crystals are monoclinic with a=17.971(13), b=13.475(3), c=13.379(8) A, β=106.67(5)°, Z=4CaO10C22H26F12, space group C2/c, d calc =1.537 g/cm3. The complex (C2 symmetry) has a molecular structure and belongs to the guest-host type. The Ca atom is located in the center of the 18-crown-6 cavity; bidentate hexafluoroacetylacetonate guest ligands occupy the trans-positions relative to the plane of a maxidentate macrocycle. The Ca−O distances in a ten-vertex Ca polyhedron are 2.474–2.666 A. The macrocycle conformation is characterized by six gauche C−C bonds and two gauche and ten trans C−O bonds. The dihedral COCC angle differs significantly (by 38.1°) from the angle of 60°, which is common to a gauche conformation. The six-membered cycle formed by oxygen atoms has a twist form with the annular O−O distances of 5.132–5.329 A. Structural features explaining an easy sublimation of the compound are discussed.