We present the synthesis and characterization of a family of partially protected block copolymers and their precursors synthesized by means of nitroxide mediated radical polymerization (NMRP) and a sequence of quantitative and orthogonal polymer analogous reactions. The target materials consist of an unprotected 4-hydroxystyrene block and a tert-butoxycarbonyl (BOC) or a tert-butyl (TBU) protected block. Corresponding precursor block copolymers exhibit low polydispersity indexes (PDI) (< 1.36) and show well-defined compositions of their blocks. Techniques like NMR, FT-IR, GPC, DSC, and TGA were applied in order to verify structure, compositions, molar masses, molecular weight distributions, and thermal properties. These materials are promising candidates for self-assembly in thin films and subsequent photolithographic patterning applications.