X‐ray absorption spectroscopy (XAS) was applied to investigate the growth behavior of LaNiO3thin films on Si substrate deposited via radio frequency magnetron sputtering at high temperature. The thickness of deposited film was always proportional to the sputtering time. However, the Ni‐to‐La ratio in the film was found to decrease with increasing substrate temperature. It is due to a loss of Ni on high‐temperature deposition which lowers the film growth rate and leads to a gradual structural change. Nevertheless, the oxidation states of both Ni atom and La atom in the thin films were not influenced by the substrate temperature or sputtering time. All the XAS evidence was consistent with the results from x‐ray reflectivity, x‐ray diffraction, and chemical analysis. ©1996 American Institute of Physics.