Polyurethane (PU) films were prepared from different types of poly(ε-caprolactone) glycols and hexamethylene diisocyanate without using any other ingredients such as solvent, catalyst, or chain extender. Polymers were stabilized by crosslinking formed as allophanate and/or biuret linkages during the curing process. The effects of different components on the product properties such as chemical structure, microphase segregation, mechanical strength, thermo-mechanical, thermal properties, and surface hydrophilicities were investigated by FTIR-ATR, atomic force microscope, mechanical tester, dynamic mechanical analyses, thermogravimetric analyzer, differential scanning calorimetry, and contact angle measurements. Phase separation of hard and soft segments significantly varied depending on the type and molecular weight of diol and triol. Films containing urethane-urea bonds displayed the maximum phase separation and the highest mechanical strength. Polyols having higher molecular weight increased hydrophilicity while urea bonds caused a reverse effect resulted by bidentate hydrogen bonds. Results showed PUs with various properties can be synthesized via environmentally friendly process without using any solvent or catalyst. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 39758.