The band alignment of atomic layer deposited (HfZrO4)1−x(SiO2)x (x = 0, 0.10, 0.15, and 0.20) gate dielectric thin films grown on Si (100) was obtained by using X-ray photoelectron spectroscopy and reflection electron energy loss spectroscopy. The band gap, valence band offset, and conduction band offset values for HfZrO4 silicate increased from 5.4 eV to 5.8 eV, from 2.5 eV to 2.75 eV, and from 1.78 eV to 1.93 eV, respectively, as the mole fraction (x) of SiO2 increased from 0.1 to 0.2. This increase in the conduction band and valence band offsets, as a function of increasing SiO2 mole fraction, decreased the gate leakage current density. As a result, HfZrO4 silicate thin films were found to be better for advanced gate stack applications because they had adequate band gaps to ensure sufficient conduction band offsets and valence band offsets to Si.