Polyurethanes were synthesized based on an amorphous polyester polyol, and different chain extenders, comparing the universally accepted symmetric chain extender (1,4-butanediol) with an asymmetric (1,2-propanediol) chain extender. The effect of incorporating a crystalline polyester polyol polyhexamethylene adipate (PHMA) was investigated. The resulting morphologies and tensile properties are dramatically different. Based on the thermal and infrared data obtained, the sample with the symmetric chain extender exhibits a phase-separated morphology, which can change as a function of time and temperature. Conversely, the polyurethane with the asymmetric chain extender has a phase mixed morphology that remains stable under the same experimental conditions. Incorporating crystalline PHMA resulted in a substantial change in the mechanical properties of the materials, especially for the copolymer comprising asymmetric chain extender. The rate of crystallization and the degree of crystallization achieved depended on the type of chain extender used. (c) 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018