The development of elastomeric, bioresorbable, and biocompatible segmented polyurethanes (SPUs) for use in tissue-engineering applications has attracted considerable interest in recent years. In this work, nonporous films and microfiber/nanofiber scaffolds, which were prepared from two different poly(Ïμ-caprolactone)-based SPUs previously synthesized from 1,6-hexamethylene diisocyanate and novel chain extenders containing urea groups or an aromatic amino acid derivative, were studied. Their thermal properties were influenced by both the different chemical structures of the hard segments and the processing conditions. The mechanical properties of the scaffolds (the elastic modulus, ultimate strain, and tensile stress) were adequate for engineered soft-tissue constructs (e.g., myocardial tissue). The film samples displayed a low swelling degree (<2 wt %) in a phosphate-buffered solution at 37°C. The introduction of the amino acid derivative chain extender with hydrolyzable ester bonds contributed to greater degradation. The fibrous scaffolds exhibited higher hydrolytic stability than the films after short assay times because of their more crystalline structures and higher degrees of association by hydrogen bonding, but they also experienced higher mass losses under accelerated conditions (70°C). This suggested that the degradation rate was not constant but depended on the degradation time and the processing technique. © 2011 Wiley Periodicals, Inc.