Linear and star shaped polyglycidols (synonym with polyglycerols) are prepared in a controlled ring opening polymerization of protected glycidols. Beside the molar mass and the polydispersity, the architecture of the polyglycidols is controlled by using mono- and multifunctional mono- and polydispers initiators. Copolymers of dissimilarly protected glycidols as well as copolymers with nonfunctional oxiranes were prepared by means of anionic polymerization while copolymers of protected glycidol with tetrahydrofuran were prepared by means of cationic polymerization. Polyethers with functional groups in the side chains (functional polyethers) with special emphasis on polyglycidols (containing hydroxymethyl groups in the side chains) were used to prepare multifunctional polymers and (hetero)grafted polymer brushes via chemical and enzyme catalyzed reaction. The potential of poly(glycidol-graft-epsilon-carpolactone)-co-glycidol) prepared via enzyme catalyzed grafting of polyglycidols using epsilon-caprolactone as a monomer and Lipase B from Candida antaretica its it catalyst is presented. Finally, comparative degradation studies of densely and loosely grafted polyglycidols are presented and discussed. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47:3209-3231, 2009