This paper will report the methods to deposit polycrystalline or amorphous chromium oxide (Cr2O3) thin films, which have potential applications in optoelectronics such as components for flat panel display devices. An atmospheric cold wall chemical vapor deposition (CVD) system was used to thermally decompose sublimed chromium acetylacetonate(Cr(C5H7O2)3) precursor, which gave Cr2O3 films. Oxygen concentration in gas phase is the key factor determining chromia film structure. In oxygen containing CVD system, the deposited films were polycrystalline Cr2O3, with (006), and (110) orientations. In inert, O2 free environment, the grown films were amorphous chromium oxide, as identified by XPS and XRD results. Based on depth profiling AES results, even in an oxygen free ambient, the elemental Cr/O ratio in films still remained stoichiometry(Cr:O = 2:3). Oxygen atoms might originate from acetylacetonyl (C5H7O2) ligands in the Cr(C5H7O2)3precursor.