The electrochemical deposition of ZnO hierarchical nanostructures directly from PHEMA hydrogel coated electrodes has been successfully demonstrated. A variety of hierarchical ZnO nanostructures, including porous nanoflakes, nanosheets and nanopillar arrays were fabricated directly from the PHEMA hydrogel coated electrodes. Hybrid ZnO-hydrogel composite films were formed with low zinc concentration and short electrodeposition time. A dual-layer structure consisting of a ZnO/polymer and pure ZnO layer was obtained with zinc concentration above 0.01 M. SEM observations and XPS depth profiling were used to investigate ZnO nanostructure formation in the early electrodeposition process. A growth mechanism to understand the formation of ZnO/hydrogel hybrid hierarchical nanostructures was developed. The I-V characteristics of the ZnO-hydrogel composite films in dark and under ultraviolet (UV) illumination demonstrate potential applications in UV photodetection.