Thin films based on scandium oxide (Sc2O3) were deposited on silicon substrates to investigate the thickness effect on the reduction of work function. X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), energy dispersive X-ray reflectivity (EDXR), atomic force microscopy (AFM), and ultraviolet photoelectron spectroscopy (UPS) measurements were performed on the films deposited by electron-beam evaporation with different nominal thicknesses (in the range of 2–50 nm) and in multi-layered mixed structures with barium fluoride (BaF2) films. The obtained results indicate that non-continuous films are required to minimize the work function (down to 2.7 eV at room temperature), thanks to the formation of surface dipole effects between crystalline islands and substrates, even if the stoichiometry is far from the ideal one (Sc/O = 0.38). Finally, the presence of BaF2 in multi-layered films is not beneficial for a further reduction in the work function.