Pure magnesium (MgO) and zinc oxide doped with aluminum oxide (Zn0.8Al0.2O) were prepared via atomic layer deposition. We have studied the structure and band gap of bulk Zn0.8Al0.2O material by X-ray diffractometer (XRD) and Tauc method, and the band offsets and alignment of atomic layer deposited MgO/Zn0.8Al0.2O heterointerface were investigated systematically using X-ray photoelectron spectroscopy (XPS) in this study. Different methodologies, such as neutralizing electron gun, the use of C 1s peak recalibration and zero charging method, were applied to recover the actual position of the core levels in insulator materials which were easily influenced by differential charging phenomena. Schematic band alignment diagram, valence band offset (Delta E-V) and conduction band offset (Delta E-C) for the interface of the MgO/Zn0.8Al0.2O heterostructure have been constructed. An accurate value of Delta E-V = 0.72 + 0.11 eV was obtained from various combinations of core levels of heterojunction with varied MgO thickness. Given the experimental band gaps of 7.83 eV for MgO and 5.29 eV for Zn0.8Al0.2O, a type-II heterojunction with a Delta E-C of 3.26 + 0.11 eV was found. Band offsets and alignment studies of these heterojunctions are important for gaining deep consideration to the design of various optoelectronic devices based on such heterointerface. (C) 2016 Elsevier B.V. All rights reserved.