We have studied the electronic structure and interfacial properties of mechanically exfoliated few-layer NiPS3 van der Waals crystals on ZnO/Nb:SrTiO3 substrates using scanning photoelectron microscopy and spectroscopy. The conducting ZnO layer enhances the visibility of few-layer NiPS3 on Nb:SrTiO3 and prevents charging effects in photoemission. We experimentally determined a type-II band alignment at the NiPS3/ZnO interface. The valence band offset (VBO) of few-layer NiPS3/ZnO is 2.8 +/- 0.09 eV, and the conduction band offset is 1.0 +/- 0.09 eV. Moreover, we found an increase of similar to 0.3 eV in VBO as decreasing NiPS3 thickness, suggesting electronic coupling or charge transfer at the NiPS3/ZnO interface. (C) 2016 Elsevier B.V. All rights reserved.