We have studied the band offset and alignment of pulsed laser deposited Al2O3/CuGaO2 and ZnO/CuGaO2 hetero-structures using photoelectron spectroscopy. Al2O3/CuGaO2 interface exhibited a type I band alignment with valance band offset (VBO) of 4.05 eV whereas type ll band alignment was observed in ZnO/CuGaO2 hetero-structure with a VBO of 2.32 eV. Schematic band alignment diagram for the interface of these hetero-structures has been constructed. Band offset and alignment studies of these heterojunctions are important for gaining insight to the design of various optoelectronic devices based on such hetero-structures. (C) 2014 Elsevier B.V. All rights reserved.