An innovative associative strategy, crystallization-driven self-assembly, is discussed for hybrid inorganicorganic materials. We report the use of a semicrystalline poly(butadiene)-b-poly(ethylene oxide)(PB-b-PEO) diblock copolymer (BCP) that self-assembles with silica nanoparticles (NPs) in a selective solvent. In ethanol, at 60 degrees C, that is above the melting temperature T-m of the PEO block, the BCP forms amorphous spherical micelles consisting of a liquid PEO-corona and a core of PB-chains. The controlled formation of hybrid structures is achieved using temperature quenches below T-m of the BCP where the PEO block crystallizes in the micellar corona, leading to the formation of lamellar structures. The crystallization further dictates the spatial distribution and drives the self-assembly of the colloidal particles into the BCP lamellar domains. Such association is tunable and reversible, following the crystallization temperature T. The employed method offers new perspectives for the directed self-assembly of colloidal particles through an underlying controlled crystallization process of semicrystalline BCP in solution. (C) 2013 Elsevier Ltd. All rights reserved.