Semiconductor nanocrystals serve as the building blocks for designing next generation solar cells, chemical/biological sensors, and metal chalcogenides (e.g., CdS, CdSe, PbS, and PbSe) are particularly useful for harnessing size-dependent optical and electronic properties in nanostructures. In this paper, relying on the interaction including van der Waals forces and hydrogen bond, CdSe/PS sub-microspheres composite and TiO2/CdSe/PS sub-microspheres with yolk-shell structure were prepared via self-assembly of CdSe quantum dots and colloidal titanium dioxide on modified PS surface. The morphology, structure and composition obtained products were investigated by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM) and energy disperse X-ray spectroscopy (EDX). Transmission electron microscopy (TEM) investigations show the CdSe quantum dots and colloidal titanate were assembled on the surface of PS sub-microspheres. CdSe QD-polymer sub-microspheres composites in which the QDs retain their original emission efficiency can be obtained. TiO2/CdSe/PS sub-microspheres with yolk-shell structure can improve the efficiency of charge separation. (C) 2015 Elsevier B.V. All rights reserved.