Poly(-caprolactone)-based graft copolymers were prepared via a grafting from technique derived from iodine transfer polymerization. This copolymerization was done thanks to a poly(-caprolactone-co--iodo--caprolactone) (PCL-I), which was used as a multisite transfer agent. Styrene (Sty) and n-butyl acrylate (n-BuA) were firstly used as model monomers to establish the feasibility of using PCL-I as multisite transfer agent, and investigate some general properties of the polymerization. The formation of PCL-g-PSty and PCL-g-P(n-BuA) copolymers was confirmed by SEC and NMR analyzes of the copolymers before and after degradation of the PCL backbone. This method was extended to an acrylamide monomer, namely (N,N-dimethyl) acrylamide (DMA), to prepare original amphiphilic copolymers with PCL as hydrophobic backbone and amido-functionalized hydrophilic grafted chains.