We demonstrated a simple route to simultaneously synthesize PdO and boehmite nanoparticles, and to directly immobilize the former on the latter using an ionic liquid (IL)-assisted one-pot solution method. PdO nanoparticles were directly immobilized on boehmite nanoparticles, and their amount and distribution were controlled by the stoichiometry of the mixture. In particular, gamma-alumina nanofibers, which were topochemically transformed from boehmites, exhibited lengths of ca. 40-70 nm and diameters of ca. 1.5-3 nm, while PdO nanoparticles had diameters of ca. 2-4 nm. The nanocrystalline structures of the PdO nanoparticles immobilized on the boehmite nanoparticles were characterized by high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), and Al-27 nuclear magnetic resonance (NMR). The one-step synthetic method described herein allows for the design and fabrication of host-guest systems of inorganic or metallic nanomaterials with hetero-nanostructures. (C) 2011 Elsevier Inc. All rights reserved.