Living anionic polymerization of an acetal protected 4-hydroxystyrene monomer, (4-(2-tetrahydropyranyloxy)styrene) (OTHPSt), and the chain extension of the poly(OTHPSt) anion with a variety of monomers including styrene, 4-tert-butylstyrene, methacryloyl polyhedral oligomeric silsesquioxane (MAPOSS) and hexamethylcyclotrisiloxane is demonstrated. The P(OTHPSt) homopolymer has a glass transition temperature well above room temperature, which facilitates handling and purification of the protected poly(4-hydroxystyrene) (PHS). The resulting diblock copolymers have narrow dispersities <1.05. Chemoselective mild deprotection conditions for the P(OTHPSt) block were identified to prevent simultaneous degradation of the MAPOSS or dimethylsiloxane (DMS) block, thus allowing for the first reported synthesis of P(HS-b-DMS) and P(HS-b-MAPOSS). (c) 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1458-1468