Shape memory polyurethanes (SMPUs) have been synthesised via a novel synthetic methodology, resulting in an improvement of the phase separation in the multi-block structure of the polyurethane and in its shape memory properties. ABA block copolymers based on semi-crystalline poly(epsilon-caprolactone) and amorphous poly(propylene oxide) (PPO) were used as precursor for the SMPUs. For their synthesis, poly(c-caprolactone) diols have been converted into isocyanate end-capped prepolymers by using a mixture of 3(4) isocyanato-1-methyl-cyclohexylisocyanate isomers, after which a coupling with low-T-g poly(propylene oxide) oligomers is done. The shape memory polymers are obtained by reaction of the ABA block copolymers with hexamethylenediisocyanate and 1,4-butanediol as chain extender. Using this new strategy, a flexible segment (PPO) was introduced between the hard and the switching segments of the SMPU. For comparison, SMPUs without flexible segment have also been prepared with the conventional synthetic route. DSC, isostrain experiments and cyclic shape memory tests revealed narrower switching temperatures for the SMPUs including a flexible segment. (C) 2009 Elsevier Ltd. All rights reserved.