UV embossing is a replication method whereby an UV-curable polymer is pressed against a patterned mold and cured with UV irradiation, resulting in a patterned polymeric substrate. High aspect ratio UV embossing will find diverse applications in tissue engineering, micro-optics, display technologies, and sensors. Demolding of an UV-embossed polymer pattern with aspect ratio of 5 from the mold has previously been demonstrated experimentally. In this paper, parameters that affect the demolding process have been identified and investigated. They include cross-linking shrinkage during curing by UV irradiation, modulus of cured polymer, interfacial fracture strength and toughness, and loading method during demolding. Shrinkage is an important parameter, and an optimum level of shrinkage to avoid breakage of the embossing (sigma(1)(max)) during demolding was found to exist. This optimum level is that at which the maximum stress, experienced by the polymer during demolding is minimized. The micromechanics of demolding was found to be different for shrinkage values lower or larger than the optimum value.