Uncrystallized indium-gallium-zinc-oxide (InGaZnO) thin-film transistors (TFTs) combined with an aluminum nitride (AlN) dielectric have been used to promote performance and steadiness. However, the high deposition temperature of AlN films limits their application in InGaZnO flexible TFTs. In this work, AlN layers were deposited via low-temperature plasma-enhanced atomic layer deposition (PEALD), and InGaZnO films were fabricated via high-power impulse magnetron sputtering (HIPIMS). The band alignment of the AlN/InGaZnO heterojunction was studied using the X-ray photoemission spectrum and ultraviolet visible transmittance spectrum. It was found that the AlN/InGaZnO system exhibited a staggered band alignment with a valence band offset ΔEv of −1.25 ± 0.05 eV and a conduction band offset ΔEc of 4.01 ± 0.05 eV. The results imply that PEALD AlN could be more useful for surface passivation than a gate dielectric to promote InGaZnO device reliability under atmospheric exposure.