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