Scandium oxide films with thickness d = 20–100 nm were deposited by atomic layer deposition (ALD) using tris(methylcyclopentadienyl) scandium (III) Sc(MeCp)3 and water vapors as precursors at reactor temperature range of 200–400 °C. The ALD-window was detected in the range of 230–370 °C. Growth per cycle remained constant and was 0.080–0.084 nm/cycle in this range. O/Sc ratio was found to be 1.49 which is close to stoichiometric Sc2O3. The films were polycrystalline. The grains were more apparent for the films grown at higher temperatures. The grain size increased with thickness. Cubic Sc2O3 phase was determined by FTIR, Raman spectroscopy and X-rays diffraction. In general, different crystallographic directions are more preferential for different process conditions. Films were textured and their growth occurred mainly in the (400) direction. The refractive index dispersions of deposited films were well described by the Cauchy model. Optical properties depended weakly on process parameters (temperature or thickness). As it was detected for the films with close thickness the refractive index slightly increased with deposition temperature increase. The Nasyrov-Gritsenko (N-G) multiphonon trap ionization model well describes the charge transport. The trap parameters were determined to be: concentration N = 1.5 × 1019 cm−3, thermal energy Wt = 0.83 eV, and optical energy Wopt = 1.66 eV.