We demonstrate a polymer brush assisted approach for the fabrication of continuous zirconium oxide (ZrO₂) films over large areas with high uniformity (pin-hole free) on copper (Cu) substrates. This approach involves the use of a thiol-terminated polymethyl methacrylate brush (PMMA-SH) as the template layer for the selective infiltration of zirconium oxynitrate (ZrN₂O₇). The preparation of a highly uniform covalently grafted polymer monolayer on the Cu substrate is the critical factor in fabricating a metal oxide film of uniform thickness across the surface. Infiltration is reliant on the chemical interactions between the polymer functional group and the metal precursor. A following reductive H₂ plasma treatment process results in ZrO₂ film formation whilst the surface Cu₂O passive oxide layer was reduced to a Cu/Cu₂O interface. Fundamental analysis of the infiltration process and the resulting ZrO₂ film was determined by XPS, and GA-FTIR. Results derived from these techniques confirm the inclusion of the ZrN₂O₇ into the polymer films. Cross-sectional transmission electron microscopy and energy dispersive X-ray mapping analysis corroborate the formation of ZrO₂ layer at Cu substrate. We believe that this quick and facile methodology to prepare ZrO₂ films is potentially scalable to other high-κ dielectric materials of high interest in microelectronic applications.