In this paper, a novel method for fabrication of core-shell nanospheres with polystyrene (PS) as the core and multi-walled carbon nanotubes (MWNTs) as the shell via hydrogen-bonding self-assembly is introduced. The PS nanospheres with carboxyl acid groups on the surface (PS-COOH nanospheres) were prepared by typical soap-free emulsion copolymerization with acrylic acid as comonomer. The MWNTs were grafted with poly(vinyl pyrrolidone) (PVP), in which the carbonyl oxygen can act as proton acceptors to form hydrogen bonds with the carboxyl acid groups. The results show that the functionalized MWNTs can self-assemble onto the surface of PS-COOH nanospheres rapidly via hydrogen bonding interaction, and the process is reversible and can be well controlled by adjusting pH value of the system. These core-shell nanospheres have the potential to be used as conductive and synergistic reinforcement fillers in fabricating high-performance and functional nanocomposites. (C) 2010 Elsevier Ltd. All rights reserved.