On the basis of a new acetal-protected glycerol monomethacrylate monomer (cis-1,3-benzylidene glycerol methacrylate/BGMA) a series of potentially biocompatible and partially biodegradable homo- and block copolymers were synthesized. ATRP polymerization of BGMA yielded well-defined polyacrylates with pendant benzylidene acetal groups and high glass transition temperatures (115-130 degrees C). This hydrophobic poly(cis-1,3-benzylidene glycerol methacrylate) could be readily transformed into the hydrophilic and water-soluble poly(1,3-dihydroxypropyl methacrylate), referred to as poly(isoglycerol methacrylate) (PIGMA). It exclusively contains primary hydroxyl groups and therefore differs significantly from the commonly known poly(glycerol methacrylate) (PGMA). Block copolymer systems based on poly(lactide) and BGMA were realized via two orthogonal living polymerization techniques starting from a bifunctional initiator, employing first atom transfer radical polymerization (ATRP) of BGMA and in the second step organo-base catalyzed polymerization of or D-lactide. This route provides well-definecl block copolymers of low polydispersity (PDI 1.12-1.17) and molecular weights in the range of 7000 to 30 000 g/mol (NMR). Rapid and highly selective acetal hydrolysis of the PBGMA block resulted in the release of the hydrophilic and water-soluble poly(1,3-dihydroxypropyl methacrylate) (poly(isoglycerol methacrylate), PIGMA). Acidic hydrolysis of the acetal protecting groups of poly(BGMA)-b-poly(lactide) copolymers proceeded smoothly to amphiphilic structures, notably without affecting the potentially labile polyester block. The novel PIGMA-b-PLLA copolymers are capable of supramolecular self-assembly to spherical aggregate structures in aqueous environment. The polymers generally exhibited low aggregation constants (CAC: 8-20 mg/L). Because of the unique feature of stereocomplex formation of poly(lactide), the corresponding aggregate morphology could be adjusted by mixing two nearly identical PIGMA-b-PLA copolymers with enantiomeric poly(lactide blocks) in a 1:1 ratio. In this case the uniformly shaped micelles (20 nm) changed to large vesicles with diameters ranging from 600 to 1400 nm. These features render this new type of amphiphilic block copolymers promising for drug delivery applications.