Three novel monomeric glyme adducts of cerium hexafluoroacetylacetonate (Ce(hfa) 3 ×diglyme 1, Ce(hfa) 3 ×diethyldiglyme 2, and Ce(hfa) 3 ×dibutyldiglyme 3) have been synthesized adopting a one-pot procedure and characterized by elemental analyses, mass spectrometry, and infrared spectroscopy. Single-crystal X-ray diffraction (XRD) studies provide evidence of a mononuclear nine-coordinated complex with a monocapped square antiprismatic structure of the Ce(hfa) 3 ×diglyme (monoclinic system, space group = P2 1 /c; a = 10.037(2) , b = 15.643(5) , c = 21.080(5) , b = 103.460(5), Z = 4). The thermal analyses of all three compounds revealed high volatility and good thermal stability with low residue. The adducts 1±3 have better mass transport properties and thermal behavior than conventional cerium metal±organic chemical vapor deposition (MOCVD) precursors, and have been successfully applied to CeO 2 film depositions. The good quality of the deposited layers indicates that the adducts are very attractive precursors for MOCVD applications.