Amphiphilic monomers containing the isomeric pyridine moieties 3-(4-vinylphenyl)pyridine (3VPPy) and 4-(4-vinylphenyl)pyridine (4VPPy) were synthesized using the Suzuki coupling reaction. A living anionic polymerization of 3VPPy and 4VPPy was successfully performed under various conditions to overcome the limitations of anionic polymerization and to compare their properties with those of poly(2-(4-vinylphenyl)pyridine) as reported previously. Several characteristics of the resulting isomeric P3VPPy and P4VPPy were studied, such as thermal stability, solubility, and the living nature. The block copolymerization of 4VPPy with 2-vinylpyridine and MMA was carried out without additive to estimate the nucleophilicity of P4VPPy and to confirm its living nature. Additionally, each amphiphilic homopolymer of P3VPPy and P4VPPy containing both a hydrophilic pyridine unit and a hydrophobic styrene unit was tested for self-assembly behavior in a mixed solvent (THF/water) and monitored with TEM and SEM. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3458-3469