The valence band discontinuity (ΔE(v)) of Y2O3/InGaZnO4 (IGZO) heterojunctions was measured by a core-level photoemission method. The Y2O3 exhibited a band gap of -6.27 eV from absorption measurements. A value of ΔE(v) = 0.44 ± 0.21 eV was obtained by using the Ga 2p3/2, Zn 2p3/2 and in 3d5/2 energy levels as references. Given the experimental bandgap of 3.2 eV for the IGZO, this would indicate a conduction band offset ΔE(c) of - 2.63 eV in the Y2O3/IGZO heterostructures and a nested interface band alignment.