The one-pot construction of polytriazole grafted with poly(ε- caprolactone) via the polymerization of 4-azido-1-(prop-2-yn-1-yloxy)butan-2-ol (N3hydroxypropargyl) and ε-caprolactone monomers is reported. For this purpose, a click reaction and ring-opening polymerization (ROP) were combined and carried out simultaneously. N3hydroxypropargyl served as both the ROP initiator and a monomer for the click polymerization. Thus, an in situ "grafting-through and from" strategy was established in one pot. CuBr and Sn(Oct)2 were utilized as dual catalysts, and the polymerization reactions were carried out at 120 C under a N2 atmosphere. © 2013 Elsevier Ltd. All rights reserved.