The pyridine-containing monomer 2-(4'-vinylbiphenyl-4-yl-pyridine (VBPPy), synthesized by the Suzuki coupling reaction, was successfully polymerized using diphenylmethylpotassium (DPM-K) as an initiator within 360 min at -78 degrees C, resulting in 100% yield and polydispersity <1.3, as with the living anionic polymerization of 2-vinylpyridine (2VP) and 2-(4-vinylphenyl)pyridine (VPPy). By the block copolymerization of VBPPy with 2VP, VPPy, and methyl methacrylate (MMA), it was proven that the nucleophilicity of living poly(2-(4'-vinylbiphenyl-4-yl)pyridine) is between that of living poly(2-(4-vinylphenyl)pyridine) and that of living poly(methyl methacrylate). Among the block copolymers, PVBPPy-b-PMMA was used to make nanocomposites in which gold (Au) nanoparticles (NPs) were present only in the PVBPPy zone of the phase-separated PVBPPy-b-PMMA) (f(VBPPy) = 0.23) film.