We describe a very simple electroless plating method that can be used to prepare Ag-coated polystyrene beads. Robust Ag nanostructures are reproducibly fabricated by soaking polystyrene 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 polystyrene beads, but by increasing the amount of butylamine, network-like Ag nanostructurres are formed that possess very broad UV/vis absorption characteristics extending from the near-UV to near-infrared regions. In conformity with the UV/vis absorption characteristics, the Ag-deposited polystyrene beads were highly efficient surface-enhanced Raman scattering (SERS) substrates, with an enhancement factor estimated using 4-aminobenzenethiol (4-ABT) as a model adsorbate to be larger than 1.1 x 10(6). On the basis of the nature of the SERS peaks of 4-ABT, those Ag-deposited polystyrene beads were confirmed, after attaching biotin groups over 4-ABT, to selectively recognize streptavidin molecules down to concentrations of 10(-11) gmL(-1) (i.e., similar to 0.2 pM). Since a number of different molecules can be used as SERS-marker molecules (such as 4-ABT), multiple bioassays are readily accomplished via SERS after attaching appropriate host or guest molecules onto them. (c) 2007 Elsevier Inc. All rights reserved.