Poly(methylmethacrylate)-poly(4-vinylpyridine) diblock copolymers were synthesized by sequential anionic polymerization. 1,1-diphenyl-3-methylpentyllithium was used as initiator and LiCl was added to the system as ligand to modify both initiator and active chain end in order to avoid side reactions. The products were characterized by H-1-NMR spectroscopy, size exclusion chromatography and differential scanning calorimetry. The block copolymers show narrow molecular weight distribution and microphase separation as indicated by the presence of two glass transition temperatures. Block copolymer formation was verified by micellization in different solvents. Also, 4-vinylpyridine block can be completely quaternized with methyl iodide as indicated by H-1-NMR and FTIR spectroscopies.