A stable Eu3+ → Eu2+ reduction is accomplished by thermal annealing in N2 ambient of Eu2O3 films deposited by magnetron sputtering on Si substrates. Transmission electron microscopy and x-ray diffraction measurements demonstrate the occurrence of a complex reactivity at the Eu2O3/Si interface, leading to the formation of Eu2+ silicates, characterized by a very strong (the measured external quantum efficiency is about 10%) and broad room temperature photoluminescence (PL) peak centered at 590 nm. This signal is much more efficient than the Eu3+ emission, mainly consisting of a sharp PL peak at 622 nm, observed in O2-annealed films, where the presence of a SiO2 layer at the Eu2O3/Si interface prevents Eu2+ formation.