AbstractComposites based on microphase-separated diblock copolymers of styrene with vinylpyridine and gold nanoparticles, in which the block copolymers play simultaneously both the role of a stabilizer preventing the aggregation of nanoparticles and a matrix providing their selective arrangement within domains of the predefined type, are obtained for the first time. The suggested approach implies no use of additional stabilizers and is efficient for both initially organic dispersed small (~5 nm) spheres and hydrasols of larger (9 × 30 nm) rodlike nanoparticles. Nanospheres are introduced into the composites via replacement of a labile stabilizer used in synthesis with the diblock copolymer, while nanorods synthesized in aqueous media by the two-stage method are incorporated via phase transfer mediated by the diblock copolymer. Films capable of microphase separation leading to the formation of vinylpyridine cylindrical domains with a diameter of tens nanometers are spin-coated from the obtained composites. The content of nanoparticles in the composites is up to 5 wt %; they are dispersed and arranged predominantly within vinylpyridine domains, with nanospheres being localized near domain boundaries, while nanorods being mainly oriented perpendicularly to the axis of cylinders.