In this paper, we have successfully fabricated TiO2/PbS heteroarchitectures with high-quality single-crystalline PbS nanostructures well-erected on electrospun TiO2 nanofibers matrices via hydro(solvo)thermal method using L-cysteine as the sulfur donor and chelating reagent. The experiment results showed that the morphology and size of secondary PbS nanostructures grown on TiO2 nanofibers can be changed significantly by utilizing two kinds of different reaction solvents (water and acetylacetone, respectively). In case of water serving as solvent, the superb cube-shaped PbS nanocrystals with the edge length ranging from 150 to 300 nm were prepared. While acetylacetone acting as solvent, the high-density PbS nanoparticles with 10-30 nm in length were obtained. And, it is interesting that PbS nanostructures were not only uniformly monodispersed but also closely attached to TiO2 nanofibers surface. What is more, the further studies suggested that the formation of TiO2/PbS heteroarchitectures might take on chelation-anchoring-nucleation-directional growth strategy. (C) 2010 Elsevier Inc. All rights reserved.