Polyester and/or polythioester grafted chitosan copolymers were synthesized. For that, poly(epsilon-caprolactone) (PCL), poly(epsilon-thiocaprolactone) (PTCL), and their copolymers were first synthesized by ring opening polymerization. Copolymers with caprolactone:thiocaprolactone (CL:TCL) molar ratios of 2:1, 1:1, 1:2 were synthesized. All of the synthesized macromolecular architectures were characterized using different spectral (Fourier transform infrared (FTIR), proton nuclear magnetic resonance (H-1-NMR), X-Ray diffraction (XRD)) and thermal (Differential scanning calorimetry (DSC), Thermogravimetric analysis (TGA)) methods. Grafting was then performed according two distinct routes: (i) using a blend of both homopolymers (PCL and PTCL) or (ii) using pre-synthesized copolymers with controlled CL:TCL ratios. Hexamethylene diisocyanate was used as a grafting/coupling agent through urethane bonds with high yield. Grafting preferentially occurred at sulfur sites. The results indicated that PTCL is more reactive and favorable than PCL for grafting onto chitosan. With the homopolymers blend grafting route, the corresponding materials mostly had a higher PTCL portion than expected. To obtain polyester grafted chitosan with a determined CL:TCL ratio, the copolymer grafting route would yield better results.