Magnetron sputtered HfO2 layers formed on a heated Si substrate were studied by spectroscopic ellipsometer (SE), x-ray diffraction (XRD), Fourier transform infrared (FTIR), and x-ray photoelectron spectroscopy (XPS) depth profiling techniques. The results show that the formation of a SiOx suboxide layer at the HfO2/Si interface is unavoidable. The HfO2 thickness and suboxide formation are highly affected by the growth parameters such as sputtering power, O-2/Ar gas ratio during sputtering, sputtering time, and substrate temperature. XRD spectra show that the deposited film has (111) monoclinic phase of HfO2, which is also supported by FTIR spectra. The atomic concentration and chemical environment of Si, Hf, and O have been measured as a function of depth starting from the surface of the sample by XPS technique. It shows that HfO2 layers of a few nanometers are formed at the top surface. Below this thin layer, Si-Si bonds are detected just before the Si suboxide layer, and then the Si substrate is reached during the depth profiling by XPS. It is clearly understood that the highly reactive sputtered Hf atoms consume some of the oxygen atoms from the underlying SiO2 to form HfO2, leaving Si-Si bonds behind.