The structure and morphology of ultra-thin zinc oxide (ZnO) films with different film thicknesses on confined polymer template were studied through X-ray reflectivity (XRR) and grazing incidence small angle X-ray scattering (GISAXS). Using magnetron sputter deposition technique ZnO thin films with different film thicknesses (<10 nm) were grown on confined polystyrene with similar to 2R(g) film thickness, where R-g similar to 20 nm (R-g is the unperturbed radius of gyration of polystyrene, defined by R-g = 0.272.root M-0, and M-0 is the molecular weight of polystyrene). The detailed internal structure, along the surface/interfaces and the growth direction of the system were explored in this study, which provides insight into the growth procedure of ZnO on confined polymer and reveals that a thin layer of ZnO, with very low surface and interface roughness, can be grown by DC magnetron sputtering technique, with approximately full coverage (with bulk like electron density) even in"nm order of thickness, in 2-7 nm range on confined polymer template, without disturbing the structure of the underneath template. The resulting ZnO-polystyrene hybrid systems show strong ZnO near band edge (NBE) and deep-level (DLE) emissions in their room temperature photoluminescence spectra, where the contribution of DLE gets relatively stronger with decreasing ZnO film thickness, indicating a significant enhancement of surface defects because of the greater surface to volume ratio in thinner films. (C) 2017 Elsevier B.V. All rights reserved.