The mononuclear title complex. bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato-O-2,O-4)(2,5,8,11,14,17-hexa-oxaoctadecane-O-2,O-5,O-8,O-11,O-14,O-17)barium, [Ba(C5HF6O2)(2)(C12H26O6)], has a geometry similar to most other structurally characterized bis(beta-diketonato)barium polyether adducts. The central Ba2+ ion has a coordination number of ten. The hexadentate polyether coordinates meridionally with the beta-diketonato ligands on opposite sides of the neutral-ligand mean plane. The Ba-O bond lengths range from 2.758(3) to 2.858(3) Angstrom. All but one of the barium to polyether oxygen bonds are longer than the corresponding bonds to the beta-diketonato ligands. The coordinative saturation of the Ba2+ ion ensures that there are no strong intermolecular interactions, consistent with the volatility of the title compound.