Selective UV sensitivity was observed in Metal-Oxide-Semiconductor structures with Si nanoclusters. Si nanocrystals and amorphous Si nanoparticles (a-Si NPs) were obtained by furnace annealing of SiOx films with x = 1.15 for 60 min in N2 at 1000 and 700 °C, respectively. XPS and TEM analysis prove phase separation and formation of Si nanocrystals in SiO2, while the a-Si NPs are formed in SiO1.7 matrix. Both types of structures show selective sensitivity to UV light; the effect is more pronounced in the structure with nanocrystals. The responsivity of the nanocrystal structure to 365 nm UV light is ~ 4 times higher than that to green light at 4 V applied to the top contact. The observed effect is explained by assuming that only short wavelength radiation generates photocarriers in the amorphous and crystalline nanoclusters.