Abstract: A plasma enhanced-chemical vapor deposition (PE-CVD) route to Fe2O3-based materials on Al2O3(0001) single crystals at moderate growth temperatures (200-400 degrees C) is reported. The use of the fluorinated Fe(hfa)(2)TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = N,N,N',N'-tetramethylethylenediamine) molecular precursor in Ar/O-2 plasmas enabled an in situ F-doping of iron oxide matrices, with a fluorine content tunable as a function of the adopted preparative conditions. Variations of the thermal energy supply enabled control of the system phase composition, resulting in gamma-Fe2O3 at 200 degrees C and alpha-Fe2O3 nanostructures at higher deposition temperatures. Notably, at 400 degrees C the formation of highly oriented alpha-Fe2O3 nanocolumns characterized by an epitaxial relation with the Al2O3(0001) substrate was observed. Beside fluorine content, phase composition and nano-organization, even the system optical properties and, in particular, energy gap values, could be tailored by proper modifications of processing parameters.