Using e-beam evaporation technique, transparent surface-hydrated lanthanum oxide (OH-La2O3) films with a thickness of 40, 140, and 545 nm were obtained. The electrical and optical characteristics of Al/OH-La2O3/p-Si structures were studied, where aluminum and a silicon substrate with p-type conductivity were used as the upper and lower electrodes, respectively. Negative differential conductivity region in the conductivity–voltage characteristics for the forward bias voltage was found; a possible mechanism of negative differential conductivity is explained by proton transport in hydrogen bonded chains of water molecules at the OH-La2O3 film surface.