RAFT polymerization was used to prepare polystyrene – poly(4-vinyl pyridine) block copolymers, PSn-b-P(4VP)m. Well-defined block copolymers were obtained despite some indications of hydrolysis of the RAFT endgroup during synthesis. The block copolymer PS70-b-P(4VP)55 was self-assembled into micellar structures in dichloromethane, leading to nanoparticles with hydrodynamic diameters of 70 nm. The micelles were loaded with HAuCl4 and, upon reduction, micellar gold-containing nanoparticles with hydrodynamic diameters of 240 nm were obtained. These nanoparticles were employed in the preparation of honeycomb-structured porous films by means of the breath figures technique to yield gold nanocomposites with a hexagonal porous array.