Mastery of the structure of nanomaterials enables control of their properties to enhance their performance for a given application. Herein we demonstrate the synthesis of metal nanomaterials with hollow interiors or cage-bell structures based on the inside-out diffusion of Ag in core-shell structured nanoparticles. It begins with the synthesis of core-shell Ag-M or core-shell-shell M-A-Ag-M-B nanoparticles in an organic solvent. Ag is then extracted from the core or the inner shell by bis(p-sulfonatophenyl)phenylphosphane, which binds strongly with Ag(I)/Ag(0) to allow the complete removal of Ag in 24-48 h, leaving behind an organosol of hollow or cage-bell structured metal nanomaterials. Because of their relatively lower densities, which usually translate to a higher surface area than their solid counterparts, the hollow and cage-bell structured metal nanomaterials are especially relevant to catalysis. For example, cage-bell structured Pt-Ru nanoparticles were found to display outstanding methanol tolerance for the cathode reaction of direct methanol fuel cells (DMFCs) as a result of the differential diffusion of methanol and oxygen in the cage-bell structure.