The LaNiO3 (LNO) thin films were deposited on Si substrate by rf magnetron sputtering. The interface and electrical properties of LNO/Si contacts were investigated. For the deposition at room temperature, an amorphous LNO film with a clean interface was formed on the Si. However, a thin silicon oxide layer of approximately 2.5 nm was formed at the interface between LNO and Si after rapid thermal annealing (RTA) at temperatures ≥450 °C. On the other hand, a highly (100)-textured LNO film along with an interfacial oxide layer of approximately 6.0 nm was obtained for the deposition at 400–450 °C. Nevertheless, if an ion beam etching was applied prior to the high temperature deposition at 400–450 °C, a clean interface at the interface could be obtained for the LNO/Si contacts. Moreover, crystallites with (111) planes grown epitaxially along the (111) planes of Si were found in the LNO films. All the contacts had shown good current–voltage characteristics of a Schottky diode with a barrier height of 0.69–0.78 eV for the LNO/n-Si contacts and 0.60–0.67 eV for the LNO/p-Si contacts, and the barrier height increased with the thickening of interfacial oxide layer. From the measurement of capacitance (C) under reverse bias (Vr) of the contacts made with LNO deposited on the ion-etched Si substrates, a linear relation was observed in the plot of C−2 against Vr except a deviation of linearity in the low-bias part of the curve. This deviation is most likely due to the segregation and inward diffusion of La and Ni near the interface of LNO/Si contacts. Nevertheless, the barrier heights evaluated from an extrapolation of linear part of the plots are reasonably consistent with those obtained from the I–V measurement.