In this paper, an Au/Ag bimetallic hollow nanostructure was obtained by using SiO(2) nanospheres as sacrificial templates. The nanostructure was fabricated via a three steps method. SiO(2)@Au nanospheres were first synthesized by the layer-by-layer technique, and then they were coated with a layer of Ag particles, finally, the Au/Ag bimetallic hollow nanospheres were obtained by dissolution of the SiO(2) core by exposure in HF solution. Several characterizations, such as transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX) and UV visible absorption spectroscopy were used to investigate the prepared nanostructures. The effectiveness of these Au/Ag bimetallic hollow nanospheres as substrates toward surface-enhanced Raman scattering (SERS) detection was evaluated by using rhodamine 6G (R6G) as a probe molecule. We show that such Au/Ag bimetallic hollow nanospheres structure films which consisting of larger interconnected aggregates are highly desirable as SERS substrates in terms of high Raman intensity enhancement. The Au/Ag bimetallic hollow nanostructured aggregate, interconnected nanostructured aggregate and nanoscale roughness are important factors responsible for this large SERS enhancement ability. (C) 2011 Elsevier B.V. All rights reserved.