This study is devoted to a thorough structural and microstructural characterization of nanophasic LaOF-based thin films. The coatings were synthesized by Chemical Vapor Deposition (CVD) onto Si(100) substrates at growth temperatures between 250 and 500 degrees C, using La(hfa)3.diglyme (Hhfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione; diglyme = bis(2-methoxyethyl)ether) as both La and F molecular source under nitrogen + wet oxygen atmospheres. The system structure and microstructure were investigated by Glancing Incidence X-ray Diffraction (GIXRD) and X-ray microdiffraction. The most relevant sample features, with particular attention to the phase composition as a function of the synthesis conditions, are critically discussed.