In this paper we describe a very simple electroless plating method used to prepare Ag-coated silica beads. Robust Ag nanostructures can be reproducibly fabricated by soaking silica beads in ethanolic solutions of AgNO3 and butylamine. When the molar ratio of butylamine to AgNO3 is far below 1.0, distinct nanosized Ag particles are formed on the silica beads, but by increasing the amount of butylamine, network-like Ag nanostructures are formed that possess very broad UV/vis absorption characteristics extending from near-UV to near-infrared regions. In conformity with the UV/vis absorption characteristics, the Ag-deposited silica beads were highly efficient surface-enhanced Raman scattering (SERS) substrates, with the enhancement factor estimated using benzenethiol as a model adsorbate to be larger than 10(6). Since another silica layer can be readily deposited onto the Ag surface, the Ag-coated silica beads should be invaluable in the development of SERS-based biosensors.