The surface relief structure of polymer films over large areas can be controlled by combining nanoscale imprinting and microscale ultraviolet-ozone (UVO) radiation, resulting in hierarchical structured surfaces. First, nanoscale patterns were formed by nanoimprinting elastomer [poly(dimethylsiloxane) (PDMS)] films with a pattern on a digital video disk. Micron-scale patterns were then superimposed on the nanoimprinted PDMS films by exposing them to ultraviolet radiation in oxygen (UVO) through a transmission electron microscopy grid mask having variable microscale patterning. UVO exposure leads to conversion and densification of PDMS to SiO , leading to micron height relief features that follow a linear scaling relation with pattern dimension. Further, the pattern scopes are shown to collapse into a master curve by normalized feature values. Interestingly, these relief structures preserve the nanoscale features. In this paper, the influence of the self-limiting PDMS densification, wall stress at the boundary of micro-depression, and UVO exposure energy is studied in control of the micro-depression scale. This simple two-step imprinting process involving both nanoimprinting and UV radiation allows for facile fabrication of the dimension adjustable micro-nano hierarchically structures not only on elastomer films but also on thermoplastic polymer films. Coarse-grained molecular dynamics simulations were performed to correlate the surface tension and elastic properties of polymeric materials to the deformation of the pattern structure.