The ubiquitous use of poly(ethylene glycol) in the biomaterials field has also boosted the research activity in the chemical derivatization of this polymer. We focused our interest on the preparation of tailor-made poly(ethylene glycol)-based structures and on the study of structure-activity relationships for its functionalization, as preliminary steps for the preparation of smart functional materials. More specifically, amphiphilic and cationic block copolymers were prepared for prospective use in the preparation of self-assembled carriers, and Michael-type addition of thiols onto acrylates was studied as a model for end-group reaction leading to hydrogel formation.