This review highlights the precise synthesis and application of various well-defined rod-coil and coil-coil block copolymers composed of poly(2-(or 4-)vinylpyridine) (P2VP or P4VP) block(s) with pyridine moieties. These polymers were synthesized by means of living anionic polymerization. Poly(hexyl isocyanate) (PHIC) was used as the rod-like segment, because hexyl isocyanate undergoes living anionic polymerization under carefully selected conditions. This review describes the syntheses of the block copolymers, polystyrene-b-P2VP, polystyrene-b-P4VP, polyisoprene-b-P2VP, NVP-b-poly(methyl methacrylate), P2VP-b-poly(ethylene oxide). P2VP-b-poly(2-(N-carbazolyl)ethyl methacrylate), P2VP-b-PHIC, P2VP-b-PHIC-b-P2VP, and PHIC-b-P2VP-b-PHIC. The formation of self-organized narrostructured materials and molecular assemblies by such block copolymers and their possible applications are also described. These assemblies include monolayers, microphase-separated periodic-ordered nanostructures, micelles, polymer-metal complexes, nanoparticles, inorganic and metal layers, and nanoporous films with nanoparticles. (C) 2009 Elsevier Ltd. All rights reserved.