Four different miktoarm star copolymers poly(ethylene glycol-(epsilon-caprolactone)(2)) diol [PEG-PCL2] were obtained using alpha-diol-omega-methoxy poly(ethylene glycol) [MPEG-(OH)(2)] as macroinitiator/chain transfer wagent in the ring opening polymerization (ROP) of epsilon-caprolactone (CL) catalyzed by tin(II) 2-ethylhexanoate [Sn(Oct)(2)]. PEG-PCL2 and 1,6-hexamethylene diisocyanate (HDI) were used as precursors of a new family of poly(ester-ether urethane)s PEUs. PEUs films were characterized by FT-IR, DSC, mechanical properties, water absorption, hydrolytic degradation and SEM. (C) 2012 Elsevier Ltd. All rights reserved.