Capitalizing on the inertness of styrene toward Grignard reagents, 4-vinylphenylmagnesium bromide was utilized for the rapid and convenient preparation of the protected monomer 2,2-dimethyl-4-(4-vinylbenzyl)-1,3-dioxolane (DMVBDO), avoiding the use of catalysts and painstaking purification protocols. Well-defined homopolymers, statistical copolymers, and block copolymers with styrene (S) as a comonomer were prepared in THE at -78 degrees C via carbanionic living polymerization. The overall molecular weights ranged from 4.5 to 68.9 kg mol(-1) with low dispersities (D 1.04-1.15). Copolymers were synthesized with styrene feed ratios (X-feed) from 15 to 95 mol % with glass transition temperatures (T-g) between 46 and 91 degrees C. Whereas polystyryllithium served as an excellent macroinitiator for the preparation of the block copolymer PS0.5-b-P(DMVBDO)(0.5), the inverse block order, i.e., synthesis of P(DMVBDO)(0.5)-b-PS0.5, yielded a bimodal molecular weight distribution (MWD) with increased dispersity, which is ascribed to slow crossover. Rapid deprotection of both homo- and copolymers to release two hydroxyl groups per DMVBDO unit was achieved via acidic hydrolysis. The deprotected block copolymer PS0.5-b-P(VPPDO)(0.5) showed phase separation, indicated by two T-g values (68 and 86 degrees C). Homogeneous brush copolymers of the type P(S-85-co-VPPDO5)-g-PLLA and P(S-85-co-VPPDO6)-g-PEO were demonstrated by using quantitative "grafting from" with L-lactide and ethylene oxide, respectively. The brush-like copolymers were obtained in quantitative yields while maintaining monodisperse MWD.