Photografting of bifunctional photolinker on biocompatible amphiphilic copolymers, such as PCL-b-PEGs and PLGA-b-PEGs, has been developed as a practical and versatile strategy for the materials functionalisation. Depending on the copolymer nature (block length, % of crystallinity) and the experimental conditions we could selectively direct the grafting on the hydrophilic PEG segments. The resulting copolymers were further derivatized with molecules of interest (RGD-peptides, LDV-peptides, “home-made”peptidomimetics, mannose derivatives,…) by substitution of the O-succinimidyl ester of the photolinker. The derivatization rates were controlled by radiolabelling, colorimetric assay and XPS spectroscopy. The functionalized copolymers were used in the formulation of nanoparticles displaying the ligands on their outer-shell. This nanoparticulate system was successfully employed for the oral vectorisation of antigen and for the targeted delivery of an anticancer drug.