Ultraviolet (UV) embossing, involving molding against micro-structured molds, is a quick and efficient method to mass produce high aspect ratio micro-features. A crucial challenge to the repeatability and large-scale application of this technique is successful demolding, which escalates in difficulty with increasing aspect ratio, due to increased polymer-mold mechanical interlocking. Some of the key factors affecting UV embossing include the crosslinked polymer shrinkage and material properties, interfacial strength between polymer to mold and the demolding method. This paper presents a new method to simulate the demolding of UV cured polymer from a nickel mold. Hyperelastic material model and rate-independent cohesive zone modeling were employed in the numerical simulation; linear elastic polymer response, although relatively easy to apply, was not adequate. Progressive shrinkage was implemented, leading to delamination of the polymer-mold interface. The subsequent peeling of the cured polymer from the mold was modeled with increasing prescribed displacement. The optimal shrinkage degree was found to increase from 0.92 to 1.9% with increasing mold aspect ratio (aspect ratio is defined as height to width ratio) from 5 to 10.