A new convenient route for the synthesis of poly(epsilon-caprolactone) (PCL) with alpha,omega-telechelic diols' end-groups is presented. Synthesis of alpha,omega-telechelic PCL diols (HOPCLOH) was achieved by ring-opening polymerization (ROP) of epsilon-caprolactone (CL) catalyzed with ammonium decamolybdate (NH4)(8)[Mo10O34] and using diethylene glycol (DEG) as initiator. Obtained HOPCLOH was characterized by H-1 and C-13 NMR, FT-IR, GPC and MALDI-TOF. Comparative studies demonstrate that ammonium decamolybdate (NH4)(8)[Mo10O34] is better catalyst than Sn-octanoate (SnOct(2)) toward CL polymerization in presence of DEG, under the conditions tested. A biodegradable poly(ester-urethane-urea) derivative was efficiently prepared from synthesized HOPCLOH. Obtained polymer shows minor differences with respect to the properties recorded for a poly(ester-urethane-urea) obtained from commercial HOPCLOH. (c) 2006 Elsevier Ltd. All rights reserved.