In this work, we study the band alignment of few-layer thick WSe₂/SiO₂ heterointerface. The few monolayer thick WSe₂ nanosheets are synthesized on 300 nm SiO₂/Si substrate by employing liquid exfoliation method. Structural and optical investigations of fabricated WSe₂ nanosheets were investigated using X-ray diffraction (XRD), Raman, valence band photoemission spectroscopy, and atomic force microscopy (AFM). By resorting to X-ray photoelectron spectroscopy (XPS) and valence band photoemission spectroscopy (VBPES) measurements, we found that WSe₂/SiO₂heterointerface Type-I band alignment. Moreover, our calculations reveal that values of valence band offset and conduction band offset at the WSe₂/SiO₂ interface were found to be 3.79 ± 0.05 and 3.21 ± 0.05 eV, respectively.