Morphologies of the poly(n-hexyl isocyanate)-block-poly(2-vniylpyridine) (PHIC-b-P2VP,f(P2VP) = 0.3) amphiphilic rod-coil block copolymer were studied in rod-selective chloroform (CHCl3), both-block-soluble tetrahydrofuran (THF), and CHCl3/THF mixed solvent systems. Spherical, solid micelles with a P2VP core and PHIC shell were formed in CHCl3, whereas a microphase-separated liquid crystalline morphology was prominent in the presence of THE In the CHCl3/THF mixed solvent system, a unique long-range intermicellar-chained network (v/v = 7/3) and a more evolved cylindrical micellar network (v/v = 3/7) were remarkably formed, respectively. PHIC-b-P2VP network nanostructures were used as a template for the in situ synthesis of Au nanoparticles (8 nm) selectively within the functional P2VP core domains.