A novel method is proposed to access to new poly(alpha-amino-epsilon-caprolactoneco-epsilon-caprolactone) using poly(alpha-iodo-epsilon-caprolactone-co-epsilon-caprolactone) as polymeric substrate. First, ring-opening (co)polymerizations of alpha-iodo-epsilon-caprolactone (alpha I epsilon CL) with epsilon-caprolactone (epsilon CL) are performed using tin 2-ethylhexanoate (Sn(Oct)(2)) as catalyst. (Co)polymers are fully characterized by H-1 NMR, C-13 NMR, FTIR, SEC, DSC, and TGA. Then, these iodinated polyesters are used as polymeric substrates to access to poly(alpha-amino-epsilon-caprolactone-co-epsilon-caprolactone) by two different strategies. The first one is the reaction of poly(alpha I epsilon CL-co-epsilon CL) with ammonia, the second one is the reduction of poly(alpha N-3 epsilon CL-co-epsilon CL) by hydrogenolysis. This poly(alpha-amino-epsilon-caprolactone-co-epsilon-caprolactone) (F-alpha NH2 epsilon CL < 0.1) opens the way to new cationic and water-soluble PCL-based degradable polyesters. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6104-6115, 2009