Replicated polydimethylsiloxane (PDMS) micro/nanostructures are widely used in various research fields due to their inexpensiveness, flexibility, low surface energy, good optical properties, biocompatibility, chemical inertness, high durability, and easy fabrication process. However, the application of PDMS micro/nanostructures is limited when an accurate pattern shape or position is required because of the shrinkage that occurs during the PDMS curing process. In this study, we analyzed the effects of processing parameters in the PDMS replication process on the shrinkage of the final structure. Although the shrinkage can be decreased by decreasing the curing temperature, this reduction also increases the unnecessary curing time. To minimize the inherent shrinkage in the PDMS replica without an accompanying curing time increase, we propose a PDMS replication process on a high modulus substrate (glass and polymer films) with compression pressure, in which the adhesion force between the substrate and the PDMS, and the compression pressure prevent shrinkage during the curing process. Using the proposed method, a PDMS replica with less than 0.1% in-plane and vertical shrinkage was obtained at a curing temperature of 150°C and a curing time of 10 min.