Porous 3D metal-nanoparticle assemblies with selectable morphologies are synthesized. Biosilica templates (diatom frustules) are first converted into silicon replicas via magnesiothermic reduction. Electroless metal deposition, followed by silicon dissolution, then yields metal-nanoparticle assemblies with the 3D template morphology (figure reveals a silver assembly; inset images reveal internal features after partial ion milling and EDX analysis).